[0001] The present invention relates to high solids aqueous mineral and/or filler and/or
pigment suspensions in acidic pH environment, to a method for producing such high
solids aqueous mineral and/or filler and/or pigment suspension, to the use of the
high solids aqueous mineral and/or filler and/or pigment suspension in paper making,
paper coating, plastic, agricultural and/or paint applications and as filler in paper
and to a coating color formulation comprising the high solids aqueous mineral and/or
filler and/or pigment suspension.
[0002] In practice, aqueous preparations and especially suspensions of water-insoluble solids
such as calcium carbonate containing materials are used extensively in the paper,
paint, rubber and plastics industries as coatings, fillers, extenders and pigments
for papermaking as well as lacquers and paints. For example, suspensions, also called
slurries of calcium carbonate, talc or kaolin are used in the paper industry in large
amounts as filler and/or as a component in the preparation of coated paper. Typical
aqueous preparations of water-insoluble solids are characterized in that they VT:MJ
comprise water, a water-insoluble dispersed solid compound and optionally further
additives in the form of a suspension or slurry.
[0003] One problem in this regard resides in the fact that the adjustment of suitable mechanical
properties for such aqueous suspensions is still a challenge under certain conditions.
Since the transport of suspensions of calcium carbonate should be economically viable,
the quantity of water in the suspension or the volume of the suspension should be
as small as possible. However, especially at low temperatures such as typically reached
in winter time the mechanical properties of such high solids aqueous suspensions significantly
worsen due to a freezing of the suspension which makes the transport and further handling
difficult. In addition thereto, high solids aqueous suspensions comprising calcium
carbonate containing material tend to be instable under acidic conditions such as
in the presence of e.g. acidic additives which can be typically part of such aqueous
suspension and, thus, result in worsen mechanical properties over time.
[0004] In this regard, several approaches for improving the mechanical properties of aqueous
suspensions comprising calcium carbonate containing material have been proposed. For
example,
WO 96/32448 describes a process for the processing of a dispersion of calcium carbonate (known
in the industry as a "slurry") with a low concentration of carbonate (1 to 30% of
solid matter) using polyDIMDAC (dimethyldiallyl ammonium homopolymer), which is a
cationic aggregating agent of low molecular weight from 10,000 to 500,000, in order
to obtain bulk. This patent uses both PCC and ground natural calcium carbonate, referred
to as "G(N)CC" or ground natural calcium carbonate, or mixtures thereof. This process
is mainly one of flocculation, an aggregation of small particles onto larger ones
and the property of interaction with the fibres is principally obtained by the exclusively
coarse granulometry of the particles. The physical properties of the paper are then
unfavourably affected when its weight diminishes.
[0005] WO 96/32449 provides broadly the same information. The aim is to obtain a selective aggregation
of fine and ultra-fine particles, using an aggregating agent presenting a charge opposed
to the overall charge of the filler.
[0006] US 4,367,207 describes a process for treating CaCO
3 in the presence of an anionic organopolyphosphonate electrolyte, but the aim is simply
to obtain a suspension of finely-divided carbonate.
[0007] EP 0 406 662 describes a process for manufacturing synthetic carbonate in which a pre-mix is made
of CaCO
3 in aragonitic form with lime; to this slurry is added a "phosphoric acid derivative"
such as phosphoric acid or its salts or various phosphates, and finally CO
2 is introduced in order to effect conventional carbonation. The purpose of this patent
is specifically to obtain a PCC with a large particle size and a particular crystalline
form (acicular), the industrial manufacture of which was not previously possible.
[0008] Phosphoric acid is used in
EP 0 406 662 in order to produce specifically the aragonitic form via an unidentified "phosphoric
acid calcium" which provides new nucleation seeds for the required crystalline form.
The carbonate products obtained are useful in paper manufacture to allow the incorporation
of greater quantities of mineral matter into the paper, producing incombustible interior
papers. No properties such as the opacity, gloss or bulk of the paper are mentioned.
Furthermore, the only application example concerns a carbonate/resin compound.
[0009] EP 1 982 759 A1 relates to a process for the purification of water, wherein a surface-reacted natural
calcium carbonate is brought into contact with the water to be purified, the surface-reacted
natural calcium carbonate being the reaction product of a natural calcium carbonate
with an acid and carbon dioxide, which is formed in situ by the acid treatment and/or
supplied externally.
[0010] EP 2 264 108 A1 relates to a process for preparing a surface-reacted calcium carbonate in an aqueous
environment. The process aims at avoiding the mandatory implementation of medium-strong
to strong acids.
EP 2 264 108 A1 is also directed to an aqueous suspension of surface-reacted calcium carbonate which
is obtainable by the process.
[0011] EP 2 264 109 A1 relates to a process for preparing surface-reacted calcium carbonate. The process
comprising the following steps: a) providing a calcium carbonate; b) providing 5 wt.-%
to 50 wt.-%, based on the weight of calcium carbonate, of at least one acid having
a pKa of less than or equal to 2.5, wherein the corresponding acid anion is capable
of forming water-insoluble calcium salts; c) providing gaseous CO
2; d) providing at least one water soluble non-polymeric organic and/or inorganic weak
acid and/or a hydrogen salt of said at least one water soluble non-polymeric organic
and/or inorganic weak acid; and e) contacting said calcium carbonate with said at
least one acid having a pKa of less than or equal to 2.5 of step b), with said gaseous
CO
2 of step c) and with said at least one water soluble non-polymeric organic and/or
inorganic weak acid and/or hydrogen salt of said at least one water soluble non-polymeric
organic and/or inorganic weak acid of step d); wherein the at least one water soluble
non-polymeric organic and/or inorganic weak acid has a pKa of greater than 2.5 and
wherein its corresponding acid anion is capable of forming water-insoluble calcium
salts.
[0012] Processes are also known for giving particular properties to the carbonate-containing
material.
[0013] We shall mention among others the obtaining of properties of resistance to acids,
which are useful when the carbonate is employed as a filler in acidic paper-making
processes, which are some of the traditional paper manufacture procedures. Thus,
US 5,043,017 describes the stabilisation of calcium carbonate, and in particular of PCC by the
action of a calcium-chelating agent such as calcium hexametaphosphate, and an associated
base which can be an alkaline metal salt of a weak acid (phosphoric, citric, boric,
acetic acid etc.).
[0014] US 4,219,590 describes a process for improving dry calcium carbonate by its treatment with a "totally
dry anhydride gas". Herein, the improvement of the surface treatment is effected by
a fatty acid or an acid resin or similar products. This process treats the carbonate
by boil-off vapours of phosphoric, hydrochloric, nitric, capric or acrylic acid or
chlorides or fluorides of aluminum, or of fumaric acid etc. The aim is to split the
carbonate particles into fine particles.
[0015] US 5,230,734 is also known, which uses CO
2 to produce a Ca-Mg carbonate.
WO 97/08247 describes a carbonate formulation, also for paper, obtained by a weak acid method.
The carbonate is treated with a mixture of a weak acid and weak base, those being
phosphoric acid and a derivative of an organic acid, respectively.
WO 97/14847 also describes a carbonate resistant to acids, for paper, which is treated with a
mixture of two weak acids in order to "de-activate" the surface of the carbonate.
[0016] WO 98/20079 also describes a process for rendering a carbonate resistant to acids, and in particular
a PCC, by adding calcium silicate and a weak acid or alum.
US 5,164,006 uses a treatment by CO
2 in order to obtain properties of resistance to an acid medium. However, the addition
of products such as zinc chloride is then necessary, which does not meet environmental
standards.
[0017] As already mentioned above, the aqueous suspensions typically comprise water, a water-insoluble
dispersed solid compound and optionally further additives in such preparations. In
this regard, it should be further noted that such dispersed calcium carbonate comprising
aqueous suspensions in combination with calcium chloride can cause serious problems
during e.g. the production of such suspension the production of a coating colour composition,
its storage, and subsequent use. If such a calcium carbonate comprising aqueous suspension
comes in contact with calcium chloride or other salts of monovalent, divalent or trivalent
cations, the formation of agglomerated and flocculated particles in the aqueous suspension
occurs which may lead to unwanted effects such as a severe worsen of mechanical properties
and/or partial dissolution of acid sensitive material in the composition.
[0018] This problem is getting worse with increasing content of calcium carbonate and/or
calcium chloride in the aqueous composition, and is especially pronounced in calcium
carbonate comprising aqueous compositions having high solids content, i.e. compositions
having solids content of more than 50 wt.-% based on the total weight of the composition.
[0019] Therefore, there is a continuous need for alternative high solids aqueous mineral
and/or filler and/or pigment suspensions which provide a better performance than existing
high solids aqueous mineral and/or filler and/or pigment suspensions and effectively
maintain the mechanical properties of a suspension at low temperature and/or in acidic
environment.
[0020] Accordingly, it is an objective of the present invention to provide an aqueous mineral
and/or filler and/or pigment suspensions having high solids content. A further objective
of the present invention is to provide a high solids aqueous mineral and/or filler
and/or pigment suspension in which the formation of agglomerated and flocculated particles
in the suspension is reduced or prevented in pH acidic environment and thus maintains
sufficient mechanical properties for such suspension. Another objective of the present
invention is to provide a high solids aqueous mineral and/or filler and/or pigment
suspension being stable in pH acidic environment, i.e. maintains sufficient mechanical
properties, over a period of at least 24 hours. An even further objective is to provide
a high solids aqueous mineral and/or filler and/or pigment suspension having sufficient
mechanical properties at temperatures of about -5 °C and even below, i.e. said suspension
does not freeze under such conditions. A still further objective is to provide a high
solids aqueous mineral and/or filler and/or pigment suspension which does not affect
the other physical properties of the suspension, such as optical properties, in an
unacceptable way. Another objective is to provide a high solids aqueous mineral and/or
filler and/or pigment suspension having an acidic pH in the presence of calcium carbonate
particles over a period of at least 24 hours, preferably over a period of at least
1 week and most preferably over a period of at least 1 month at a storage temperature
between -5 °C to +23 °C.
[0021] The foregoing and other objectives are solved by a high solids aqueous mineral and/or
filler and/or pigment suspension in acidic pH environment comprising:
- a) at least one calcium carbonate-containing material comprising calcium carbonate-containing
particles, and
- b) at least one salt of at least one strong acid, wherein the at least one strong
acid forming the at least one salt of at least one strong acid is selected from the
group consisting of acids having a pKa value of less than or equal to zero at +23 °C,
wherein the high solids aqueous suspension has
i) a solids content of at least 50 wt.-%, based on the total weight of the high solids
aqueous suspension,
ii) a Brookfield viscosity at 100 rpm of ≤ 1 000 mPas at a temperature of -5 °C
iii) a pH of < 6 at +23 °C, and
iv) a conductivity of between 10 and 100 mS/cm at -5 °C and at +23 °C, and wherein
the high solids aqueous suspension comprises the at least one salt of at least one
strong acid in an amount from 1 to 20 wt.-%, based on the total weight of the high
solids aqueous suspension.
[0022] The inventors surprisingly found that the foregoing high solids aqueous mineral and/or
filler and/or pigment suspension according to the present invention leads to a suspension
in which the formation of agglomerated and flocculated particles in the suspension
is reduced or prevented in pH acidic environment and thus maintains sufficient mechanical
properties for such suspension and, furthermore, provides for a stability in acidic
environment over a period of at least 24 hours. It was further observed that the high
solids aqueous mineral and/or filler and/or pigment suspension has an acidic pH in
the presence of calcium carbonate particles over a period of at least 24 hours at
a storage temperature between -5 °C to +23 °C. Furthermore, the inventors found out
that the high solids aqueous mineral and/or filler and/or pigment suspension does
not freeze at temperatures of about -5 °C and even below and does not affect the other
properties of the suspension, such as the optical properties, in an unacceptable way.
In particular, this is achieved by the use of a combination of at least one calcium
carbonate-containing material and at least one salt of at least one strong acid in
a high solids aqueous mineral and/or filler and/or pigment suspension having solids
content of at least 50 wt.-% based on the total weight of the high solids aqueous
suspension. Thus, the instant high solids aqueous mineral and/or filler and/or pigment
suspension enables the provision of a high solids aqueous suspension being stable
in acidic environment.
[0023] It should be understood that for the purposes of the present invention, the following
terms have the following meaning:
For the purpose of the present invention, the term "suspension" or "slurry" comprises
insoluble solids and water and optionally further additives and usually contains large
amounts of solids and, thus, is more viscous and generally of higher density than
the liquid from which it is formed.
The term "pH acidic environment" in the meaning of the present invention refers to
a high solids aqueous mineral and/or filler and/or pigment suspensions having a pH
of < 6 at +23 °C.
The term "calcium carbonate-containing material" in the meaning of the present invention
refers to a material that comprises "calcium carbonate-containing particles", at least
one "comb polymer" and optionally at least one salt of at least one strong acid. Accordingly,
the "calcium carbonate-containing material" corresponds to the total dry weight of
solid material in the high solids aqueous mineral and/or filler and/or pigment suspension.
The term "calcium carbonate-containing particles" refers to a material that comprises
at least 50 wt.-% calcium carbonate, based on the total dry weight of the calcium
carbonate-containing particles.
[0024] In the meaning of the present invention, the term "comb polymer" refers to a comb-shaped
polymer which is formed from a main chain, also referred to as back bone, to which
carbonic acid groups and/or other acid groups are attached in the form of free acids
or salts thereof, i.e. in a form of a carboxylate ion, as well as side chains comprising
polyalkylene oxide, optionally end-caped with a hydrocarbon chain. The polyalkylene
oxide side chains can be bonded to the main chain via ester bonds, amide bonds, or
ether bonds. In addition to the carbonic acid groups and the polyalkylene oxide side
chains, further functional or non-functional groups can be bonded to the main chain,
e.g. positively charged functional groups such as amine, amide and/or quaternary ammonium
groups.
[0025] The term "acid" in the present invention is defined according to the Brønsted-Lowry
definition. In other words, an acid is defined as a substance that can act as proton
donor. This means, that for example, the term "HSO
4-" also exemplifies an acid.
[0026] For the purposes of the present invention, the term "viscosity" refers to Brookfield
viscosity. According to the present invention the Brookfield viscosity is measured
using a RVT model Brookfield™ viscometer at a temperature of +23 °C and -5 °C, and
a rotation speed of 100 rpm (revolutions per minute) with the appropriate disc spindle
No 1 to 5. The reported viscosity values are the values detected by the instrument
after 1 minute of measurement. Before measuring the Brookfield viscosity the suspension
was stirred for 5 minutes using a Pendraulik laboratory dissolver, 0.25 - 2.5 kW,
mechanically adjustable up to 8400 rpm with an appropriate tooth disc stirrer.
[0027] "Conductivity" according to the present invention shall mean the electrical conductivity
of an aqueous carbonate-comprising material suspension as measured according to the
measurement method defined in the examples section here below. The conductivity is
specified in mS/cm and may be measured at -5 °C and at +23 °C.
[0028] According to another aspect of the present invention, a method for producing a high
solids aqueous mineral and/or filler and/or pigment suspension is provided, comprising
the steps of
a) providing an aqueous suspension comprising at least one calcium carbonate-containing
material, wherein the calcium carbonate-containing material has a charge density of
between +2 and -2 C/g at pH 9,
b) providing
i) at least one strong acid selected from the group consisting of acids having a pKa value of less than or equal to zero at +23 °C, and/or
ii) at least one salt of at least one strong acid, wherein the at least one strong
acid forming the at least one salt of at least one strong acid is selected from the
group consisting of acids having a pKa value of less than or equal to zero at +23 °C,
c) adding the at least one strong acid and/or the at least one salt of at least one
strong acid of step b) to the aqueous suspension comprising at least one calcium carbonate-containing
material of step a),
d) optionally grinding the aqueous suspension comprising at least one calcium carbonate-containing
material of step a) before and/or during and/or after step c),
wherein the high solids aqueous suspension after step c) and/or d) has
i) a solids content of at least 50 wt.-%, based on the total weight of the high solids
aqueous suspension,
ii) a Brookfield viscosity at 100 rpm of ≤ 1 000 mPas at a temperature of -5 °C
iii) a pH of < 6 at +23 °C, and
iv) a conductivity of between 10 and 100 mS/cm at -5 °C and at +23 °C, and wherein
the high solids aqueous suspension comprises the at least one salt of at least one
strong acid in an amount from 1 to 20 wt.-%, based on the total weight of the high
solids aqueous suspension.
[0029] It is preferred that the method further comprises step e) of providing at least one
medium strong acid selected from the group consisting of acids having a pK
a value of between 0 and 2.5 at +23 °C, preferably the at least one medium strong acid
is selected from H
2SO
3, HSO
4-, H
3PO
4, oxalic acid and mixtures thereof, and/or at least one weak acid selected from the
group consisting of acids having a pK
a value of between >2.5 to 6 at +23 °C, preferably the at least one weak acid is selected
from citric acid and/or tartaric acid. It is also preferred that the method further
comprises step f) of contacting the aqueous suspension comprising at least one calcium
carbonate-containing material of step a) with the at least one medium strong acid
and/or at least one weak acid of step e) during and/or after step c), and/or during
and/or after optional step d). It is further preferred that step c) and/or step d)
and/or step f) is carried out at a temperature of between -5 °C and +99 °C, preferably
between +20 °C and +85 °C and most preferably between +20 °C and +50 °C and most preferably
between +50 °C and +85 °C. It is also preferred that the method further comprises
step g) of concentrating the obtained high solids aqueous mineral and/or filler and/or
pigment suspension. It is also preferred that the method further comprises drying
the obtained high solids aqueous mineral and/or filler and/or pigment suspension.
[0030] According to a further aspect of the present invention, a calcium carbonate-containing
material obtainable by drying the high solids aqueous mineral and/or filler and/or
pigment suspension is provided. According to still another aspect of the present invention,
the use of the high solids aqueous mineral and/or filler and/or pigment suspension
and/or the calcium carbonate-containing material in paper making, paper coating, plastic,
agricultural and/or paint applications is provided. According to a still further aspect
of the present invention, the use of the high solids aqueous mineral and/or filler
and/or pigment suspension and/or the calcium carbonate-containing material as filler
in paper is provided. It is preferred that the high solids aqueous mineral and/or
filler and/or pigment suspension and/or the calcium carbonate-containing material
is used as a support for digital printing, preferred ink jet printing, or for flexo,
rotogravure and/or offset printing, most preferably for black ink printing in inkjet
printing.
[0031] According to a further aspect of the present invention, a coating color formulation
comprising the high solids aqueous mineral and/or filler and/or pigment suspension
and/or the calcium carbonate-containing material and a natural and/or synthetic binder
is provided, the binder preferably consisting of styrene-butadiene, styrene-acrylate,
polyvinyl acetate, polyvinyl alcohol, starch or mixtures thereof, and most preferably
the binder contains or consists of polyvinyl alcohol.
[0032] Advantageous embodiments of the present invention are defined in the corresponding
sub-claims.
[0033] According to one embodiment of the present invention, the calcium carbonate-containing
particles of the at least one calcium carbonate-containing material are selected from
among natural calcium carbonate, precipitated calcium carbonate or mixtures thereof.
[0034] According to another embodiment of the present invention, the calcium carbonate-containing
particles of the at least one calcium carbonate-containing material have a weight
median particle size
d50 from 0.1 to 50 µm, preferably from 0.25 to 50 µm, more preferably from 0.3 to 5 µm,
and most preferably from 0.4 to 3 µm.
[0035] According to yet another embodiment of the present invention, the calcium carbonate-containing
particles of the at least one calcium carbonate-containing material have a specific
surface area of from 0.1 m
2/g to 200 m
2/g, preferably from 0.1 m
2/g to 50 m
2/g and more preferably from 0.1 m
2/g to 20 m
2/g, measured using nitrogen and the BET method.
[0036] According to one embodiment of the present invention, the high solids aqueous suspension
comprises the at least one calcium carbonate-containing material in an amount of at
least 50 wt.-%, preferably from 50 to 82 wt.-%, more preferably from 55 to 82 wt.-%,
even more preferably from 60 to 78 wt.-% and most preferably from 65 to 78 wt.-%,
based on the total weight of the high solids aqueous suspension.
[0037] According to another embodiment of the present invention, the at least one calcium
carbonate-containing material comprises at least one comb polymer, preferably the
surface of the calcium carbonate-containing particles of the at least one calcium
carbonate-containing material are coated with the at least one comb polymer.
[0038] According to yet another embodiment of the present invention, the at least one calcium
carbonate-containing material comprises at least one comb polymer having an intrinsic
viscosity in the range of 5 to 99 ml/g, preferably in the range of 10 to 80 ml/g and
most preferably in the range of 10 to 50 ml/g.
[0039] According to one embodiment of the present invention, the at least one salt of at
least one strong acid comprises a divalent and/or trivalent cation, preferably the
divalent cation is selected from the group consisting of calcium, magnesium, strontium
and mixtures thereof and/or the trivalent cation preferably is aluminum.
[0040] According to another embodiment of the present invention, the at least one strong
acid forming the at least one salt of at least one strong acid is selected from the
group consisting of hydrochloric acid, nitric acid and mixtures thereof.
[0041] According to yet another embodiment of the present invention, the high solids aqueous
suspension comprises at least one comb polymer in an amount from 0.01 to 5 wt.-%,
based on the total dry weight of the calcium carbonate-containing material in the
suspension, preferably from 0.05 to 4 wt.-%, more preferably from 0.1 to 3 wt.-%,
even more preferably from 0.2 to 2 wt.-%, and most preferably from 0.25 to 1.5 wt.-%
or from 0.5 to 1.25 wt.-%.
[0042] According to one embodiment of the present invention, the high solids aqueous suspension
has solids content from 50 to 82 wt.-%, preferably from 55 to 82 wt.-%, more preferably
from 60 to 78 wt.-% and most preferably from 65 to 78 wt.-%, based on the total weight
of the high solids aqueous suspension.
[0043] According to another embodiment of the present invention, the high solids aqueous
suspension has a Brookfield viscosity at 100 rpm from 25 to 1 000 mPas at a temperature
of -5 °C, preferably from 25 to 700 mPas at -5 °C, more preferably from 25 to 500
mPas at -5 °C and most preferably from 50 to 300 mPas at -5 °C.
[0044] According to yet another embodiment of the present invention, the high solids aqueous
suspension has a pH of between 4 and < 6 at +23 °C, preferably a pH of between 4.5
and < 6 at +23 °C and preferably a pH of between 5 and < 6 at +23 °C.
[0045] According to one embodiment of the present invention, the high solids aqueous suspension
has a conductivity of between 20 mS/cm and 100 mS/cm measured at -5 °C and +23 °C
and preferably between 30 mS/cm and 100 mS/cm measured at -5 °C and +23 °C.
[0046] According to another embodiment of the present invention, the high solids aqueous
suspension further comprises at least one reaction product or products of the at least
one calcium carbonate-containing material with at least one medium strong acid and/or
at least one reaction product or products of the at least one calcium carbonate-containing
material with at least one weak acid. It is preferred that the at least one medium
strong acid forming the at least one reaction product or products of the at least
one calcium carbonate-containing material is selected from the group consisting of
acids having a pK
a value of between 0 and 2.5 at +23 °C, preferably the at least one medium strong acid
is selected from H
2SO
3, HSO
4-, H
3PO
4, oxalic acid and mixtures thereof. It is noted that HSO
4- can be added in the form of the alkali or earth alkali salt, and preferably in the
form of the Na, Li, K, Mg, and Ca salt. It is further preferred that the at least
one weak acid forming the at least one reaction product or products of the at least
one calcium carbonate-containing material is selected from the group consisting of
acids having a pK
a value of between >2.5 and 6 at +23 °C, preferably the at least one weak acid is selected
from citric acid, tartaric acid and mixtures thereof.
[0047] According to yet another embodiment of the present invention, the molar quantity
of the sum, expressed by the generated H
3O
+ ions, of the at least one medium strong acid forming the at least one reaction product
or products of the at least one calcium carbonate-containing material and/or the at
least one weak acid forming the at least one reaction product or products of the at
least one calcium carbonate-containing material and the at least one strong acid forming
the at least one salt of at least one strong acid relative to the quantity of moles
of CaCO
3 is in total between 0.01 and 1.9.
[0048] According to one embodiment of the present invention, the high solids aqueous suspension
further comprises aluminum hydroxide and/or magnesium hydroxide.
[0049] According to another embodiment of the present invention, the high solids aqueous
suspension has a positive charge density at pH 5, preferably of at least +0.1 C/g
at pH 5, more preferably of at least +0.5 C/g at pH 5, even more preferably of at
least +1 C/g at pH 5 and most preferably of at least +1.5 C/g at pH 5.
[0050] In the following, it is referred to further details of the present invention and
especially the foregoing components of the high solids aqueous mineral and/or filler
and/or pigment suspension.
[0051] Where the term "comprising" is used in the present description and claims, it does
not exclude other non-specified elements of major or minor functional importance.
For the purposes of the present invention, the term "consisting of" is considered
to be a preferred embodiment of the term "comprising of". If hereinafter a group is
defined to comprise at least a certain number of embodiments, this is also to be understood
to disclose a group, which preferably consists only of these embodiments.
[0052] Whenever the terms "including" or "having" are used, these terms are meant to be
equivalent to "comprising" as defined above.
[0053] Where an indefinite or definite article is used when referring to a singular noun,
e.g. "a", "an" or "the", this includes a plural of that noun unless something else
is specifically stated.
[0054] One specific requirement of the present invention is that the high solids aqueous
mineral and/or filler and/or pigment suspension in acidic pH environment comprises
at least one calcium carbonate-containing material. In particular, the at least one
calcium carbonate-containing material comprises calcium carbonate-containing particles.
[0055] According to one embodiment of the present invention, the calcium carbonate-containing
particles being part of the at least one calcium carbonate-containing material are
selected from among natural calcium carbonate, precipitated calcium carbonate or mixtures
thereof.
[0056] "Ground calcium carbonate" (GCC) in the meaning of the present invention is a calcium
carbonate obtained from natural sources, such as limestone, marble, calcite, dolomite
or chalk, and processed through a wet and/or dry treatment such as grinding, screening
and/or fractionating, for example by a cyclone or classifier.
[0057] A ground calcium carbonate (GCC) may feature, e.g. one or more of marble, limestone,
chalk, and/or dolomite. According to one embodiment of the present invention the GCC
is obtained by dry grinding. According to another embodiment of the present invention
the GCC is obtained by wet grinding and subsequent drying.
[0058] In general, the grinding step can be carried out with any conventional grinding device,
for example, under conditions such that refinement predominantly results from impacts
with a secondary body, i.e. in one or more of: a ball mill, a rod mill, a vibrating
mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition
mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter,
or other such equipment known to the skilled man. In case the calcium carbonate-containing
particles comprise wet ground calcium carbonate-containing particles, the grinding
step may be performed under conditions such that autogenous grinding takes place and/or
by horizontal ball milling, and/or other such processes known to the skilled man.
The wet processed ground calcium carbonate-containing particles thus obtained may
be washed and dewatered by well known processes, e.g. by flocculation, filtration
or forced evaporation prior to drying. The subsequent step of drying may be carried
out in a single step such as spray drying, or in at least two steps. It is also common
that such calcium carbonate-containing particles undergo a beneficiation step (such
as a flotation, bleaching or magnetic separation step) to remove impurities.
[0059] "Precipitated calcium carbonate" (PCC) in the meaning of the present invention is
a synthesized material, generally obtained by precipitation following reaction of
carbon dioxide and lime in an aqueous environment or by precipitation of a calcium
and carbonate ion source in water.
[0060] A precipitated calcium carbonate (PCC) may feature, e.g. one or more of aragonitic,
vateritic and/or calcitic mineralogical morphological forms. The aragonitic morphology
is commonly in the acicular form, whereas vateritic morphology belongs to the hexagonal
crystal system. The calcitic morphology can form scalenohedral, prismatic, spheral
and rhombohedral forms. PCC can be produced in different ways, e.g. by precipitation
with carbon dioxide, the lime soda process, or the Solvay process in which PCC is
a by-product of ammonia production. The obtained PCC slurry can be mechanically dewatered
and dried.
[0061] It is preferred that the calcium carbonate-containing particles comprise ground calcium
carbonate (GCC). For example, the calcium carbonate-containing particles comprise
one ground calcium carbonate (GCC). Alternatively, the calcium carbonate-containing
particles comprise a mixture of two or more ground calcium carbonates (GCC) selected
from different sources of ground calcium carbonate. For example, the calcium carbonate-containing
particles comprise one ground calcium carbonate (GCC) selected from dolomite and one
ground calcium carbonate (GCC) selected from marble.
[0062] In one preferred embodiment of the present invention, the calcium carbonate-containing
particles comprise a mixture of ground calcium carbonate and a precipitated calcium
carbonate.
[0063] In addition to calcium carbonate, the calcium carbonate-containing particles may
comprise further metal oxides such as titanium dioxide and/or aluminium trioxide,
metal hydroxides such as aluminium tri-hydroxide and/or magnesium hydroxide, metal
salts such as sulfates, silicates such as talc and/or kaolin clay and/or mica, carbonates
such as magnesium carbonate and/or gypsum, satin white and mixtures thereof.
[0064] According to one embodiment of the present invention, the amount of calcium carbonate
in the calcium carbonate-containing particles being part of the at least one calcium
carbonate-containing material is at least 50 wt.-%, e.g. at least 60 wt.-%, preferably
between 50 and 100 wt.-%, more preferably between 60 and 99 wt.-% and most preferably
between 70 and 98 wt.-%, based on the total dry weight of the calcium carbonate-containing
particles.
[0065] According to one embodiment of the present invention, the amount of calcium carbonate-containing
particles in the at least one calcium carbonate-containing material is at least 50
wt.-%, preferably at least 75 wt.-%, more preferably at least 80 wt.-%, and most preferably
at least 88 wt.-% or at least 99.9 wt.-%, based on the total dry weight of the calcium
carbonate-containing material. For example, the amount of calcium carbonate-containing
particles in the at least one calcium carbonate-containing material is between 85
wt.-% and 99.9 wt.-%, based on the total dry weight of the calcium carbonate-containing
material.
[0066] Additionally or alternatively, the high solids aqueous mineral and/or filler and/or
pigment suspension comprises the at least one calcium carbonate-containing material
in an amount of at least 50 wt.-%, preferably from 50 to 82 wt.-%, more preferably
from 55 to 82 wt.-%, even more preferably from 60 to 78 wt.-% and most preferably
from 65 to 78 wt.-%, based on the total weight of the high solids aqueous suspension.
[0067] According to one embodiment of the present invention, the calcium carbonate-containing
particles of the at least one calcium carbonate-containing material have a weight
median particle size
d50 from 0.1 to 50 µm, preferably from 0.25 to 50 µm, more preferably from 0.3 to 5 µm,
and most preferably from 0.4 to 3 µm, as measured by Sedigraph 5120.
[0068] For example, the calcium carbonate-containing particles of the at least one calcium
carbonate-containing material have a weight median particle size d
50 from 0.4 to 0.3 µm or from 0.4 to 2.0 µm, as measured by Sedigraph 5120.
[0069] Throughout the present document, the "particle size" of the calcium carbonate-containing
particles is described by its distribution of particle sizes. The value d
x represents the diameter relative to which x % by weight of the particles have diameters
less than
dx. This means that the
d20 value is the particle size at which 20 wt.-% of all particles are smaller, and the
d75 value is the particle size at which 75 wt.-% of all particles are smaller. The
d50 value is thus the weight median particle size, i.e. 50 wt.-% of all grains are bigger
or smaller than this particle size. For the purpose of the present invention the particle
size is specified as weight median particle size
d50 unless indicated otherwise. For determining the weight median particle size
d50 value for particles having a
d50 value between 0.4 and 2 µm, a Sedigraph 5120 device from the company Micromeritics,
USA, can be used. For measuring the size distribution and weight median diameter
d50 by the Sedigraph, the samples were pre-diluted to the right concentration by using
deionized water but no further additives, such as usually added dispersants like polyphosphate
or polyacrylate.
[0070] Additionally or alternatively, the fraction of the calcium carbonate-containing particles
of the at least one calcium carbonate-containing material having a particle size of
less than 2 µm is greater than 60 wt.-%, preferably greater than 70 wt.-%, more preferably
greater than 80 wt.-%, still more preferably greater than 85 wt.-% and most preferably
about 90 wt.-%, based on the total weight of the at least one calcium carbonate-containing
particles, as measured with a Sedigraph 5120.
[0071] For example, the fraction of the calcium carbonate-containing particles having a
particle size of less than 0.2 µm is greater than 5 wt.-%, preferably greater than
7.5 wt.-%, more preferably greater than 10 wt.-%, still more preferably greater than
12.5 wt.-% and most preferably about 16 wt.-%, based on the total weight of the at
least one calcium carbonate-containing particles, as measured with a Sedigraph 5120.
[0072] According to one embodiment of the present invention, the calcium carbonate-containing
particles of the at least one calcium carbonate-containing material have a specific
surface area of from 0.1 m
2/g to 200 m
2/g, preferably from 0.1 m
2/g to 50 m
2/g and more preferably from 0.1 m
2/g to 20 m
2/g, measured using nitrogen and the BET method.
[0073] For example, the calcium carbonate-containing particles are marble having a specific
surface area of from 0.1 m
2/g to 200 m
2/g, preferably from 0.1 m
2/g to 50 m
2/g and more preferably from 0.1 m
2/g to 20 m
2/g, measured using nitrogen and the BET method and a weight median particle size
d50 from 0.1 to 50 µm, from 0.25 to 50 µm, or from 0.3 to 5 µm, preferably from 0.4 to
3 µm, as measured by Sedigraph 5120.
[0074] A further requirement of the present invention is that the calcium carbonate-containing
material used for preparing the high solids aqueous mineral and/or filler and/or pigment
suspension has a charge density of between +2 and -2 C/g at pH 9. In one embodiment
of the present invention, the at least one calcium carbonate-containing material used
for preparing the high solids aqueous mineral and/or filler and/or pigment suspension
has a charge density of between -0.01 and -2 C/g at pH 9, preferably of between -0.1
and -1 C/g at pH 9, more preferably of between -0.2 and - 0.8 C/g at pH 9 and most
preferably of between -0.3 and -0.7 C/g at pH 9.
[0075] It is preferred that the at least one calcium carbonate-containing material comprises
at least one comb polymer, i.e. the at least one calcium carbonate-containing material
comprises at least one kind of comb polymer.
[0076] The at least one comb polymer is preferably a comb-shaped polymer which is formed
from a main chain, also referred to as back bone, and at least one side chain attached
thereto.
[0077] Without being bound to any theory, it is believed that the at least one comb polymer
is adsorbed to the weakly positively charged particles of the calcium carbonate-containing
particles due to its negatively charged main chain, also called polymer back bone.
Furthermore, the side chains of the adsorbed at least one comb polymer cause a steric
and/or osmotic repulsion between the particles, which may lead to a steric and/or
osmotic stabilization of at least a part of the particles in the high solids aqueous
suspension.
[0078] Accordingly, the surface of the calcium carbonate-containing particles being part
of the at least one calcium carbonate-containing material is preferably at least partially
coated with the at least one comb polymer.
[0079] The expression "at least one" or "at least one kind of" comb polymer means that one
or more kinds of comb polymers may be part of the at least one calcium carbonate-containing
material in the high solids aqueous mineral and/or filler and/or pigment suspension.
[0080] According to one preferred embodiment of the present invention, the at least one
calcium carbonate-containing material being part of the high solids aqueous mineral
and/or filler and/or pigment suspension comprises only one kind of comb polymer. According
to another embodiment of the present invention, the at least one calcium carbonate-containing
material being part of the high solids aqueous mineral and/or filler and/or pigment
suspension comprises a mixture of at least two kinds of comb polymers.
[0081] Accordingly, it is also appreciated that the high solids aqueous mineral and/or filler
and/or pigment suspension comprises only one kind of comb polymer. According to another
embodiment of the present invention, the high solids aqueous mineral and/or filler
and/or pigment suspension comprises a mixture of at least two kinds of comb polymers.
[0082] It is preferred that the at least one comb polymer of the present invention is at
least one anionically charged comb polymer, i.e. the at least one comb polymer of
the present invention is at least one kind of anionically charged comb polymer.
[0083] The term "anionically charged" as used in the present invention is to be understood
to mean that the comb polymer has a total or net charge that is negative, i.e. the
sum of all positive and negative charges is negative. In other words, the polymer
must possess an excess of anionically charged functional groups or residues. This
means that the at least one anionically charged comb polymer being part of the at
least one calcium carbonate-containing material of the present invention may comprise
both positively and negatively charged functional groups or residues, i.e. cationic
and anionic functional groups or residues, as long as the total or net charge is negative,
i.e. the comb polymer is anionic. For example, the at least one anionically charged
comb polymer being part of the at least one calcium carbonate-containing material
may comprise only anionically charged functional groups or residues or may comprise
anionically and cationically charged functional groups or residues such that the total
or net charge of the at least one comb polymer is negative.
[0084] In one embodiment of the present invention, the at least one comb polymer is at least
one anionically charged comb polymer having a specific charge of -10 to -250 C/g at
pH 9, preferably from -10 C/g to -200 C/g at pH 9 and most preferably from -10 C/g
to -150 C/g at pH 9.
[0085] For example, the at least one comb polymer is at least one anionically charged comb
polymer having a specific charge from -20 C/g to -100 C/g at pH 9, preferably from
- 30 C/g to -100 C/g at pH 9 and most preferably from -30 C/g to - 70 C/g at pH 9.
[0086] According to one embodiment of the present invention, the at least one calcium carbonate-containing
material comprises at least one comb polymer having an intrinsic viscosity in the
range of 5 to 99 ml/g, preferably in the range of 10 to 80 ml/g and most preferably
in the range of 10 to 50 ml/g.
[0087] Additionally or alternatively, it is preferred that the at least one comb polymer
has a specific charge of -10 to -250 C/g at pH 9 and an intrinsic viscosity in the
range of 5 to 99 ml/g. It is further preferred that the at least one comb polymer
has a specific charge from -10 C/g to -200 C/g at pH 9 and an intrinsic viscosity
in the range of 10 to 80 ml/g. It is even further preferred that the at least one
anionically charged comb polymer has a specific charge from -10 C/g to -150 C/g at
pH 9 and an intrinsic viscosity in the range of 10 to 50 ml/g.
[0088] For example, it is preferred that the at least one comb polymer has a specific charge
from -20 C/g to -100 C/g at pH 9 and an intrinsic viscosity in the range of 10 to
50 ml/g or a specific charge from -30 C/g to -100 C/g at pH 9 and an intrinsic viscosity
in the range of 10 to 50 ml/g. In one embodiment of the present invention, the at
least one comb polymer has a specific charge from -30 C/g to -70 C/g at pH 9 and an
intrinsic viscosity in the range of 10 to 50 ml/g.
[0089] Comb polymers that may be suitable in the present invention are described in e.g.
US 2009/0199741 A1,
US 6,387,176 B1,
EP 1136508 A1,
EP 1138697 A1,
EP 1189955 A1,
US 6,946,510 B1,
US 7,514,488 B1 and
EP 0736553 A1. These documents disclose processes to produce comb polymer as well as their use
in mineral based binders such as cement. Suitable comb polymer are also described
in the product brochure "SIKA ViscoCrete
®, selbstverdickender Beton SCC" available on the website www.sika.ch.
[0090] Examples of comb polymers that may be used for the at least one calcium carbonate-containing
material being part of the high solids aqueous suspension of the present invention
are polymers of the MELFLUX
® or MelPers
® series, e.g. MelPers
® 2450 by BASF (Trostberg, Germany), ETHACRYL
® M dispersant by CoAtex, LLC (Chester, SC) or MIGHTY EG
® dispersant by Kao Specialties Americas, LLC, (High Point, NC).
[0091] In general, the average molecular weight M
w of the at least one comb polymer may vary in broad range and is typically in a range
between 10 000 and 100 000 g/mol, preferably between 20 000 and 75 000 g/mol and most
preferably between 25 000 and 50 000 g/mol.
[0092] In one preferred embodiment of the present invention, the high solids aqueous mineral
and/or filler and/or pigment suspension comprises the at least one comb polymer in
amount from 0.01 to 5 wt.-%, based on the total dry weight of the calcium carbonate-containing
material in the suspension, preferably from 0.05 to 4 wt.-%, more preferably from
0.1 to 3 wt.-%, even more preferably from 0.2 to 2 wt.-%, and most preferably from
0.25 to 1.5 wt.-% or from 0.5 to 1.25 wt.-%. For example, the high solids aqueous
mineral and/or filler and/or pigment suspension comprises the at least one comb polymer
in an amount from 0.6 to 1.1 wt.-% or from 0.7 to 1 wt.-%, based on the total dry
weight of the calcium carbonate-containing material in the suspension.
[0093] Additionally or alternatively, the at least one calcium carbonate-containing material
comprises the at least one comb polymer in amount from 0.01 to 5 wt.-%, based on the
total dry weight of the calcium carbonate-containing material in the suspension, preferably
from 0.05 to 4 wt.-%, more preferably from 0.1 to 3 wt.-%, even more preferably from
0.2 to 2 wt.-%, and most preferably from 0.25 to 1.5 wt.-% or from 0.5 to 1.25 wt.-%.
For example, the at least one calcium carbonate-containing material comprises the
at least one comb polymer in an amount from 0.6 to 1.1 wt.-% or from 0.7 to 1 wt.-%,
based on the total dry weight of the calcium carbonate-containing material in the
suspension.
[0094] One further requirement of the inventive high solids aqueous mineral and/or filler
and/or pigment suspension is that the suspension comprises at least one salt of at
least one strong acid.
[0095] In particular, it is noted that the at least one strong acid forming the at least
one salt of at least one strong acid is selected from the group consisting of acids
having a pK
a value at 23 °C of less than or equal to 0.
[0096] The expression "at least one" salt of at least one strong acid means that one or
more salts of at least one strong acid may be present in the high solids aqueous mineral
and/or filler and/or pigment suspension.
[0097] According to one preferred embodiment of the present invention, only one salt of
at least one strong acid is present in the high solids aqueous mineral and/or filler
and/or pigment suspension comprising the at least one calcium carbonate-containing
material. According to another embodiment of the present invention, a mixture of at
least two salts of at least one strong acid is present in the high solids aqueous
mineral and/or filler and/or pigment suspension comprising the at least one calcium
carbonate-containing material.
[0098] Furthermore, the expression at least one salt of "at least one" strong acid means
that salts of one or more strong acids may be present in the high solids aqueous mineral
and/or filler and/or pigment suspension.
[0099] According to one preferred embodiment of the present invention, at least one salt
of only one strong acid is present in the high solids aqueous mineral and/or filler
and/or pigment suspension comprising the at least one calcium carbonate-containing
material. According to another embodiment of the present invention, at least one salt
of a mixture of at least two strong acids is present in the high solids aqueous mineral
and/or filler and/or pigment suspension comprising the calcium carbonate-containing
material.
[0100] With regard to the cationic part of the at least one salt of at least one strong
acid, it should be noted that any divalent and/or trivalent cation is suitable as
cationic part of the at least one salt of at least one strong acid. In particular,
any divalent and/or trivalent cation is suitable as cationic part of the at least
one salt of at least one strong acid which provides a water soluble salt of the at
least one strong acid forming the at least one salt of at least one strong acid.
[0101] The term "divalent cation" in the meaning of the present invention refers to a cation
having a valency of two, e.g. a metal cation having two valencies.
[0102] The term "trivalent cation" in the meaning of the present invention refers to a cation
having a valency of three, e.g. a metal cation having three valencies.
[0103] For example, the at least one salt of at least one strong acid comprises a divalent
cation selected from the group consisting of calcium, magnesium, strontium and mixtures
thereof. Additionally or alternatively, the at least one salt of at least one strong
acid comprises aluminum as trivalent cation.
[0104] Preferably, the cationic part of the at least one salt of at least one strong acid
is derived from the at least one calcium carbonate-containing material. It is thus
appreciated that the at least one salt of at least one strong acid comprises at least
calcium as cationic part of the at least one salt of at least one strong acid.
[0105] In one preferred embodiment of the present invention, the at least one salt of at
least one strong acid comprises only calcium as cationic part of the at least one
salt of at least one strong acid. In another preferred embodiment of the present invention,
the at least one salt of at least one strong acid comprises calcium and magnesium
and/or aluminum as cationic part of the at least one salt of at least one strong acid.
[0106] Furthermore, there are no specific restrictions regarding the at least one strong
acid forming the at least one salt of at least one strong acid as long as said at
least one strong acid is selected from the group consisting of acids having a pK
a value of less than or equal to zero at +23 °C.
[0107] Preferably, any strong acid forming the at least one salt of at least one strong
acid is suitable which provides a water soluble salt of the at least one strong acid
forming the at least one salt of at least one strong acid with the at least one calcium
carbonate-containing material, that is to say at least the majority, preferably at
least 75 wt.-%, more preferably at least 90 wt.-% and most preferably at least 96
wt.-% of the total amount of the at least one salt of at least one strong acid is
dissolved within the water phase of the high solids aqueous mineral and/or filler
and/or pigment suspension.
[0108] The term "dissolved" or "water soluble" in the meaning of the present invention refers
to systems in which no discrete solid particles of the at least one salt of at least
one strong acid are observed in the solvent.
[0109] According to one preferred embodiment of the present invention, the at least one
strong acid forming the at least one salt of at least one strong acid is selected
from the group consisting of hydrochloric acid, nitric acid and mixtures thereof.
[0110] For example, the at least one strong acid forming the at least one salt of at least
one strong acid is hydrochloric acid.
[0111] The amount of the at least one salt of at least one strong acid in the high solids
aqueous mineral and/or filler and/or pigment suspension may vary in a broad range.
However, the high solids aqueous mineral and/or filler and/or pigment suspension comprises
the at least one salt of at least one strong acid in an amount from 1 to 20 wt.-%,
preferably from 2 to 15 wt.-%, more preferably from 3 to 12.5 wt.-% and most preferably
from 4 to 10 wt.-%, based on the total weight of the high solids aqueous suspension.
[0112] Optionally, the high solids aqueous mineral and/or filler and/or pigment suspension
further comprises further additives.
[0113] For example, the high solids aqueous mineral and/or filler and/or pigment suspension
further comprises at least one reaction product or products of the at least one calcium
carbonate-containing material with at least one medium strong acid.
[0114] The expression "at least one" reaction product or products means that one or more
reaction product or products may be present in the high solids aqueous mineral and/or
filler and/or pigment suspension.
[0115] According to one embodiment of the present invention, only one reaction product of
the at least one calcium carbonate-containing material with at least one medium strong
acid is present in the high solids aqueous mineral and/or filler and/or pigment suspension.
According to another embodiment of the present invention, a mixture of at least two
reaction products of the at least one calcium carbonate-containing material with at
least one medium strong acid is present in the high solids aqueous mineral and/or
filler and/or pigment suspension.
[0116] In particular, it is preferred that the at least one medium strong acid forming the
at least one reaction product or products with the at least one calcium carbonate-containing
material is chosen from amongst acids having a pK
a value of between 0 and 2.5 at +23 °C.
[0117] In one embodiment of the present invention, the at least one medium strong acid forming
the at least one reaction product or products with the at least one calcium carbonate
containing material is chosen from amongst medium strong acids forming divalent and/or
trivalent cation salts. It is preferred that the at least one medium strong acid forming
the at least one reaction product or products with the at least one calcium carbonate
containing material is chosen from amongst medium strong acids forming divalent and/or
trivalent cation salts, which are almost insoluble in water, that is to say with a
solubility of less than 0.01% by weight acids having a pK
a value of between 0 and 2.5 at +23 °C.
[0118] For example, the at least one medium strong acid forming the at least one reaction
product or products with the at least one calcium carbonate containing material is
chosen from amongst medium strong acids forming divalent and/or trivalent cation salts,
such as calcium and/or magnesium and/or aluminium salts.
[0119] In one embodiment of the present invention, the at least one medium strong acid forming
the at least one reaction product or products with the at least one calcium carbonate
containing material is selected from H
2SO3, HSO
4-, H
3PO
4, oxalic acid and mixtures thereof. For example, the at least one medium strong acid
forming at least one reaction product or products with the at least one calcium carbonate
containing material is selected from HSO
4- and/or H
3PO
4.
[0120] For example, the high solids aqueous mineral and/or filler and/or pigment suspension
further comprises at least one reaction product or products of the at least one calcium
carbonate-containing material with at least one weak acid.
[0121] The expression "at least one" reaction product or products means that one or more
reaction product or products may be present in the high solids aqueous mineral and/or
filler and/or pigment suspension.
[0122] According to one embodiment of the present invention, only one reaction product of
the at least one calcium carbonate-containing material with at least one weak acid
is present in the high solids aqueous mineral and/or filler and/or pigment suspension.
According to another embodiment of the present invention, a mixture of at least two
reaction products of the at least one calcium carbonate-containing material with at
least one weak acid is present in the high solids aqueous mineral and/or filler and/or
pigment suspension.
[0123] In particular, it is preferred that the at least one weak acid forming the at least
one reaction product or products with the at least one calcium carbonate-containing
material is chosen from amongst acids having a pK
a value of between >2.5 and 6 at +23 °C.
[0124] In one embodiment of the present invention, the at least one weak acid forming the
at least one reaction product or products with the at least one calcium carbonate
containing material is chosen from amongst weak acids forming monovalent and/or divalent
and/or trivalent cation salts. It is preferred that the at least one weak acid forming
the at least one reaction product or products with the at least one calcium carbonate
containing material is chosen from weak acids forming divalent and/or trivalent cation
salts, which are soluble in water, that is to say with a solubility of above 0.01
% by weight acids having a pK
a value of between 0 and 2.5 at +23 °C.
[0125] For example, the at least one weak acid forming the at least one reaction product
or products with the at least one calcium carbonate containing material is chosen
from amongst weak acids forming divalent and/or trivalent cation salts, such as calcium
and/or magnesium and/or aluminium salts.
[0126] In one embodiment of the present invention, the at least one weak acid forming the
at least one reaction product or products with the at least one calcium carbonate
containing material is selected from citric acid, tartaric acid and mixtures thereof.
For example, the at least one weak acid forming the at least one reaction product
or products with the at least one calcium carbonate containing material is selected
from citric acid or tartaric acid.
[0127] According to one embodiment of the present invention, the molar quantity of the sum,
expressed by the generated H
3O
+ ions, of the at least one medium strong acid forming the at least one reaction product
or products of the at least one calcium carbonate-containing material and/or the at
least one weak acid forming the at least one reaction product or products of the at
least one calcium carbonate-containing material and the at least one strong acid forming
the at least one salt of at least one strong acid relative to the quantity of moles
of CaCO
3 is in total between 0.01 and 1.9.
[0128] For example, the molar quantity of the sum, expressed by the generated H
3O
+ ions, of the at least one medium strong acid forming the at least one reaction product
or products of the at least one calcium carbonate-containing material and/or the at
least one weak acid forming the at least one reaction product or products of the at
least one calcium carbonate-containing material and the at least one strong acid forming
the at least one salt of at least one strong acid relative to the quantity of moles
of CaCO
3 is in total between 0.05 and 1 and most preferably between 0.5 and 1.
[0129] With regard to the amount of the at least one reaction product or products of the
at least one calcium carbonate-containing material with at least one medium strong
acid and/or with at least one weak acid in the high solids aqueous mineral and/or
filler and/or pigment suspension it should be noted that the amount may vary in a
broad range. However, the high solids aqueous mineral and/or filler and/or pigment
suspension comprises the at least one reaction product or products of the at least
one calcium carbonate-containing material with at least one medium strong acid and/or
with at least one weak acid in an amount from 1 to 20 wt.-%, preferably from 2 to
15 wt.-%, more preferably from 3 to 12.5 wt.-% and most preferably from 4 to 10 wt.-%,
based on the total weight of the high solids aqueous suspension.
[0130] Additionally or alternatively, the high solids aqueous mineral and/or filler and/or
pigment suspension may further comprise aluminum hydroxide and/or magnesium hydroxide.
[0131] In one embodiment of the present invention, the high solids aqueous mineral and/or
filler and/or pigment suspension comprises aluminum hydroxide and/or magnesium hydroxide
in an amount from 0.1 to 20 wt.-%, preferably from 0.1 to 15 wt.-%, more preferably
from 1 to 12.5 wt.-% and most preferably from 1 to 10 wt.-%, based on the total weight
of the high solids aqueous suspension.
[0132] The high solids aqueous mineral and/or filler and/or pigment suspension in acidic
pH environment according to the present invention comprises at least one calcium carbonate-containing
material as defined above and at least one salt of at least one strong acid as defined
above. The solids content of the high solids aqueous mineral and/or filler and/or
pigment suspension is at least 50 wt.-%, based on the total weight of the high solids
aqueous suspension.
[0133] According to one preferred embodiment of the present invention, the high solids aqueous
suspension has solids content from 50 to 82 wt.-%, preferably from 55 to 82 wt.-%,
more preferably from 60 to 78 wt.-% and most preferably from 65 to 78 wt.-%, based
on the total weight of the high solids aqueous suspension.
[0134] The inventive high solids aqueous mineral and/or filler and/or pigment suspension
does not freeze at temperatures of -5 °C or even below and thus features an advantageous
Brookfield viscosity at such low temperature compared to suspensions described in
the prior art. It is thus appreciated that the Brookfield viscosity of the high solids
aqueous mineral and/or filler and/or pigment suspension at 100 rpm is ≤ 1 000 mPas
at a temperature of -5 °C.
[0135] According to the present invention, the Brookfield viscosity is measured after 5
minutes of stirring by the use of an RVT model Brookfield™ viscometer at a temperature
of about -5°C and about +23 °C, and a rotation speed of 100 rpm (revolutions per minute)
with the appropriate disc spindle No 1 to 5. The reported viscosity values are the
values detected by the instrument after 1 minute of measurement.
[0136] According to one preferred embodiment of the present invention, the high solids aqueous
mineral and/or filler and/or pigment suspension has a Brookfield viscosity at 100
rpm from 25 to 1 000 mPas at a temperature of -5 °C, preferably from 25 to 700 mPas
at -5 °C, more preferably from 25 to 500 mPas at -5 °C and most preferably from 50
to 300 mPas at -5 °C.
[0137] In one preferred embodiment of the present invention, the Brookfield viscosity of
the high solids aqueous mineral and/or filler and/or pigment suspension measured at
-5 °C and at 100 rpm is equal to the Brookfield viscosity of the high solids aqueous
mineral and/or filler and/or pigment suspension measured at +23 °C and at 100 rpm.
[0138] For the purposes of the present application, the Brookfield viscosity is considered
as being equal if the Brookfield viscosity at -5 °C and +23 °C and measured at the
same time at 100 rpm do not differ by more than 100 mPas, preferably by not more than
75 mPas and most preferably by not more than 50 mPas.
[0139] For example, the Brookfield viscosity at 100 rpm of the high solids aqueous mineral
and/or filler and/or pigment suspension is ≤ 1 000 mPas at -5 °C and at +23 °C, preferably
from 25 to 1 000 mPas at -5 °C and at +23 °C, more preferably preferably from 25 to
700 mPas at -5 °C and at +23 °C, even more preferably from 25 to 500 mPas at -5 °C
and at +23 °C and most preferably from 50 to 300 mPas at -5 °C and at +23 °C.
[0140] It is a further requirement of the instant invention that the high solids aqueous
mineral and/or filler and/or pigment suspension has a pH of < 6 at +23 °C. Preferably,
the high solids aqueous mineral and/or filler and/or pigment suspension has a pH of
< 6 at +23 °C measured after 24 hours after preparation of the high solids aqueous
mineral and/or filler and/or pigment suspension.
[0141] According to one preferred embodiment of the present invention, the high solids aqueous
suspension has a pH of between 4 and < 6 at +23 °C, preferably a pH of between 4.5
and < 6 at +23 °C and preferably a pH of between 5 and < 6 at +23 °C. Preferably,
the high solids aqueous suspension has a pH between 4 and < 6 at +23 °C, preferably
a pH of between 4.5 and < 6 at +23 °C and preferably a pH of between 5 and < 6 at
+23 °C measured after 24 hours after preparation of the high solids aqueous mineral
and/or filler and/or pigment suspension.
[0142] The high solids aqueous mineral and/or filler and/or pigment suspension especially
features a low electrical conductivity at -5 °C and at +23 °C. It is preferred that
the high solids aqueous mineral and/or filler and/or pigment suspension has a conductivity
of between 10 and 100 mS/cm at -5 °C and at +23 °C.
[0143] According to one preferred embodiment of the present invention, the conductivity
of the high solids aqueous mineral and/or filler and/or pigment suspension is between
20 mS/cm and 100 mS/cm measured at -5 °C and at +23 °C and preferably between 30 mS/cm
and 100 mS/cm measured at -5 °C and at +23 °C.
[0144] In one preferred embodiment of the present invention, the conductivity of the high
solids aqueous mineral and/or filler and/or pigment suspension at -5 °C is equal to
the conductivity of the high solids aqueous mineral and/or filler and/or pigment suspension
at +23 °C.
[0145] For the purposes of the present application, the conductivity is considered as being
equal if the conductivity at -5 °C and +23°C and measured at the same time do not
differ by more than 30 mS/cm, preferably by more than 20 mS/cm and most preferably
by more than 15 mS/cm.
[0146] In one embodiment of the present invention, the high solids aqueous suspension has
a positive charge density in acidic pH environment, preferably at pH 5. For example,
the high solids aqueous suspension has a positive charge density of at least +0.1
C/g at pH 5, preferably of at least +0.5 C/g at pH 5, more preferably of at least
+1 C/ at pH 5 and most preferably of at least +1.5 C/g at pH 5.
[0147] It is appreciated that the high solids aqueous mineral and/or filler and/or pigment
suspension may be dried in order to obtain the calcium carbonate-containing material.
The drying of the high solids aqueous mineral and/or filler and/or pigment suspension
can be accomplished by any conventional means known to the skilled person, for example,
thermally, e.g. by means of a spray drier or a microwave or in an oven, or mechanically,
e.g. by filtration, or lowering the water content.
[0148] If the high solids aqueous mineral and/or filler and/or pigment suspension is dried,
the water content of the obtained calcium carbonate-containing material is preferably
below 5 wt.-%, more preferably below 4 wt.-%, even more preferably below 3 wt.-% and
most preferably below 2 wt.-%, based on the total dry weight of the calcium carbonate-containing
material. For example, the water content of the obtained calcium carbonate-containing
material is below 1 wt.-% or below 0.5 wt.-%, based on the total dry weight of the
calcium carbonate-containing material.
[0149] In view of the advantageous properties of the high solids aqueous mineral and/or
filler and/or pigment suspension, especially the exceptional mechanical properties
expressed by a Brookfield viscosity at 100 rpm of ≤ 1 000 mPas at a temperature of
- 5 °C and stability in acidic pH environment, the inventive high solids aqueous mineral
and/or filler and/or pigment suspension is suitable in a broad variety of applications.
[0150] In view of the very good results regarding the mechanical and optical properties
of the high solids aqueous mineral and/or filler and/or pigment suspension as defined
above, a further aspect of the present invention is the use of said high solids aqueous
suspension and/or the calcium carbonate-containing material obtained by drying said
high solids aqueous suspension in paper making, paper coating, plastic, agricultural
and/or paint applications. In one embodiment of the present invention, the high solids
aqueous mineral and/or filler and/or pigment suspension and/or the calcium carbonate-containing
material obtained by drying said high solids aqueous suspension is used as a support
for digital printing, preferred ink jet printing, or for flexo, rotogravure and/or
offset printing, most preferably for black ink printing in inkjet printing.
[0151] According to a further aspect of the present invention, the high solids aqueous mineral
and/or filler and/or pigment suspension and/or the calcium carbonate-containing material
obtained by drying said high solids aqueous suspension can be used as filler in paper.
[0152] According to another aspect of the present invention, a coating color formulation
comprising the high solids aqueous mineral and/or filler and/or pigment suspension
and/or the calcium carbonate-containing material obtained by drying said high solids
aqueous suspension is provided.
[0153] It is preferred that the coating color formulation comprises the high solids aqueous
mineral and/or filler and/or pigment suspension as defined above and/or the calcium
carbonate-containing material obtained by drying said high solids aqueous suspension
as defined above and a natural and/or synthetic binder.
[0154] According to one preferred embodiment of the present invention, the natural and/or
synthetic binder consists of styrene-butadiene, styrene-acrylate, polyvinyl acetate,
polyvinyl alcohol, starch or mixtures thereof. Preferably, the natural and/or synthetic
binder contains or consists of polyvinyl alcohol.
[0155] If the natural and/or synthetic binder comprises a mixture of at least two natural
and/or synthetic binders, one binder is preferably polyvinyl alcohol or polyvinyl
acetate and a further binder is starch and/or carboxymethyl cellulose.
[0156] With regard to the amount of the natural and/or synthetic binder in the coating color
formulation comprising the high solids aqueous mineral and/or filler and/or pigment
suspension and/or the calcium carbonate-containing material obtained by drying said
high solids aqueous suspension it should be noted that the amount may vary in a broad
range as long as a sufficient binding capacity is achieved. However, it is preferred
that the coating color formulation comprises the natural and/or synthetic binder in
an amount between 2.5 and 20 wt.-% and preferably between 5 and 17 wt.-%, based on
the total dry weight of the coating color formulation.
[0157] In particular, it should be noted that the aforementioned advantageous properties
of the high solids aqueous mineral and/or filler and/or pigment suspension are not
obtained if the at least one calcium carbonate containing material as defined above
is contacted with calcium chloride. Accordingly, the high solids aqueous mineral and/or
filler and/or pigment suspension is preferably obtainable by the method for producing
a high solids aqueous mineral and/or filler and/or pigment suspension described below.
[0158] According to another aspect of the present invention, a method for producing an aqueous
calcium carbonate containing composition is provided, comprising the steps of
a) providing an aqueous suspension comprising at least one calcium carbonate-containing
material, wherein the calcium carbonate-containing material has a charge density of
between +2 and -2 C/g at pH 9,
b) providing
i) at least one strong acid selected from the group consisting of acids having a pKa value of less than or equal to zero at +23 °C, and/or
ii) at least one salt of at least one strong acid, wherein the at least one strong
acid forming the at least one salt of at least one strong acid is selected from the
group consisting of acids having a pKa value of less than or equal to zero at +23 °C
c) adding the at least one strong acid and/or the at least one salt of at least one
strong acid of step b) to the aqueous suspension comprising at least one calcium carbonate-containing
material of step a),
d) optionally grinding the aqueous suspension comprising at least one calcium carbonate-containing
material of step a) before and/or during and/or after step c),
wherein the high solids aqueous suspension after step c) and/or d) has
i) a solids content of at least 50 wt.-%, based on the total weight of the high solids
aqueous suspension,
ii) a Brookfield viscosity at 100 rpm of ≤ 1 000 mPas at a temperature of -5 °C,
iii) a pH of < 6 at +23 °C, and
iv) a conductivity of between 10 and 100 mS/cm at -5 °C and at +23 °C, and wherein
the high solids aqueous suspension comprises the at least one salt of at least one
strong acid in an amount from 1 to 20 wt.-%, based on the total weight of the high
solids aqueous suspension.
[0159] In one preferred embodiment of the present invention, the method further comprises
step e) of providing at least one medium strong acid selected from the group consisting
of acids having a pK
a value of between 0 and 2.5 at +23 °C, preferably the at least one medium strong acid
is selected from H
2SO
3, HSO
4-, H
3PO
4, oxalic acid and mixtures thereof, and/or at least one weak acid selected from the
group consisting of acids having a pK
a value of between >2.5 to 6.0 at +23 °C, preferably the at least one weak acid is
selected from citric acid and/or tartaric acid.
[0160] If the instant invention comprises step e) of providing at least one medium strong
acid and/or at least one weak acid, the method preferably further comprises step f)
of contacting the aqueous suspension comprising at least one calcium carbonate-containing
material of step a) with the at least one medium strong acid and/or at least one weak
acid during and/or after step c), and/or during and/or after optional step d).
[0161] The addition of the at least one strong acid and/or the at least one salt of at least
one strong acid to the aqueous suspension comprising a calcium carbonate-containing
material of step c) and the optional contacting of the aqueous suspension comprising
a calcium carbonate-containing material of step f) can be accomplished by any conventional
means known to the skilled person. Preferably, the addition and/or contacting is/are
carried out under mixing and/or homogenizing and/or particle dividing conditions.
The skilled person will adapt these mixing and/or homogenizing and/or particle dividing
conditions such as the mixing speed, dividing, and temperature according to his process
equipment.
[0162] For example, the mixing and homogenizing may take place by means of a ploughshare
mixer as e.g. already described above.
[0163] It is one specific requirement of the instant method that the aqueous suspension
comprising a calcium carbonate-containing material is provided first such that the
at least one strong acid and/or the at least one salt of at least one strong acid
is added to the aqueous suspension comprising a calcium carbonate-containing material.
Accordingly, it is appreciated that method step c) is carried out in that the at least
one strong acid and/or the at least one salt of at least one strong acid is dosed
into the aqueous suspension comprising a calcium carbonate-containing material.
[0164] According to one embodiment of the present invention, the aqueous suspension comprising
a calcium carbonate-containing material of step a) is ground in optional method step
d). If the calcium carbonate-containing material being part of the aqueous suspension
of step a) comprises ground calcium carbonate particles, the aqueous suspension of
step a) is preferably wet ground in optional method step d).
[0165] In one embodiment of the present invention, the aqueous suspension of step a) comprises
a calcium carbonate-containing material comprising ground calcium carbonate particles
which is obtained by grinding, preferably wet grinding, a calcium carbonate-containing
material in method step d) and method steps c) and optional method step f) are independently
carried out before and/or during and/or after grinding, preferably wet grinding, the
calcium carbonate-containing material in method step d). Preferably, method steps
c) and optional method step f) are carried out after grinding, preferably wet grinding,
the calcium carbonate containing material of the aqueous suspension in method step
d).
[0166] The method step c) and/or step d) and/or step f) may be carried out at a temperature
of between -5 °C and +99 °C, preferably between +20 °C and +85 °C and most preferably
between +20 °C and +50 °C and most preferably between +50 °C and +85 °C.
[0167] According to one embodiment of the present invention, method step c) and/or step
d) and/or step f) may be carried out for at least 1 s, preferably for at least 1 min,
e.g. for at least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, or 10
hours.
[0168] It is preferred that the addition of the at least one strong acid and/or the at least
one salt of at least one strong acid of step b) to the aqueous suspension comprising
at least one calcium carbonate-containing material of step a) according to method
step c) is carried out after optional method step d). Accordingly, method step c)
is carried out after optional method step d).
[0169] If optional method step f) is carried out, it is preferred that the contacting of
the aqueous suspension comprising the calcium carbonate containing material of step
a) with the at least one medium strong acid and/or at least one weak acid of step
e) is carried out after the addition of the at least one strong acid and/or the at
least one salt of at least one strong acid of step b) to the aqueous suspension comprising
at least one calcium carbonate-containing material of step a) according to method
step c). Accordingly, optional method step f) is carried out after method step c).
[0170] According to one embodiment of the present invention, the aqueous suspension comprising
a calcium carbonate containing material of step a) is contacted with further additives
known to the skilled person. For example, the aqueous suspension comprising a calcium
carbonate containing material of step a) is further contacted with aluminium hydroxide
and/or magnesium hydroxide, preferably in form of a dry product or suspension.
[0171] Preferably, the contacting of the aqueous suspension comprising a calcium carbonate
containing material of step a) with the at least one further additive is carried out
before and/or during and/or after step c) and/or before and/or during and/or after
optional step d) and/or before and/or during and/or after optional step f). Preferably,
the contacting of the aqueous suspension comprising a calcium carbonate containing
material of step a) with the at least one further additive is carried out after step
c) and/or after optional step d) and/or after optional step f).
[0172] The high solids aqueous mineral and/or filler and/or pigment suspension obtained
according to the inventive method described above may be concentrated with any method
known in the art according to method step g) which is suitable for lowering the water
content of the obtained high solids aqueous mineral and/or filler and/or pigment suspension.
The high solids aqueous mineral and/or filler and/or pigment suspension may be concentrated
in method step g), for example, thermally or mechanically for lowering the water content.
For example, the high solids aqueous suspension may be concentrated such that the
solids content in the obtained aqueous suspension is at least 60 wt.-%, preferably
65 wt.-%, more preferably 70 wt.-% and most preferably 75 wt.-%, based on the total
weight of the obtained high solids aqueous suspension.
[0173] The high solids aqueous mineral and/or filler and/or pigment suspension obtained
according to the inventive method described above may be dried with any suitable method
known in the art such that a calcium carbonate-containing material is obtained. The
high solids aqueous mineral and/or filler and/or pigment suspension may be dried,
for example, thermally, e.g. by means of a spray drier or a microwave or in an oven,
or mechanically, e.g. by filtration.
[0174] The inventive high solids aqueous mineral and/or filler and/or pigment suspension
can be mixed with water to obtain a diluted aqueous mineral and/or filler and/or pigment
suspension of the inventive high solids aqueous mineral and/or filler and/or pigment
suspension.
[0175] The scope and interest of the invention will be better understood based on the following
examples which are intended to illustrate certain embodiments of the invention and
are non-limitative.
Examples
1. Measurement methods
pH measurement
[0176] The pH is measured at +23 °C using a Mettler Toledo Seven Easy pH meter and a Mettler
Toledo InLab
® Expert Pro pH electrode. A three point calibration (according to the segment method)
of the instrument is first made using commercially available buffer solutions having
pH values of 4, 7 and 10 at +20 °C (from Aldrich). The reported pH values are the
endpoint values detected by the instrument (the endpoint is when the measured signal
differs by less than 0.1 mV from the average over the last 6 seconds).
Brookfield viscosity
[0177] The Brookfield viscosity was measured by using a RVT model Brookfield™ viscometer
at a temperature of +23 °C and -5 °C, and a rotation speed of 100 rpm (revolutions
per minute) with the appropriate disc spindle from No 1 to 5. The reported viscosity
values are the values detected by the instrument after 1 minute of measurement. Before
measuring the Brookfield viscosity the suspension was stirred for 5 minutes using
a Pendraulik laboratory dissolver, 0.25 - 2.5 kW, mechanically adjustable up to 8400
rpm with an appropriate tooth disc stirrer.
Electrical conductivity measurement
[0178] The conductivity of a suspension was measured at -5 °C and +23 °C using Mettler Toledo
Seven Multi instrumentation equipped with the corresponding Mettler Toledo conductivity
expansion unit and a Mettler Toledo InLab
® 730 conductivity probe, directly following stirring this suspension at 1 500 rpm
using a Pendraulik tooth disc stirrer.
[0179] The instrument was first calibrated in the relevant conductivity range using commercially
available conductivity calibration solutions from Mettler Toledo. The influence of
temperature on conductivity was automatically corrected by the linear correction mode.
[0180] Measured conductivities are reported for the reference temperature of +23 °C. The
reported conductivity values are the endpoint values detected by the instrument (the
endpoint is when the measured conductivity differs by less than 0.4 % from the average
over the last 6 seconds).
Particle size distribution (mass % particles with a diameter < X) and weight median
grain diameter (d50) of particulate material
[0181] Weight median grain diameter and grain diameter mass distribution of a particulate
material were determined via the sedimentation method, i.e. an analysis of sedimentation
behaviour in a gravimetric field. The measurement was made with a Sedigraph
™ 5120.
[0182] The method and the instrument are known to the skilled person and are commonly used
to determine grain size of fillers and pigments. The samples were pre-diluted to the
right concentration by using deionized water but no further additives, such as usually
added dispersants like polyphosphate or polyacrylate as, and dispersed by using a
high speed stirrer and ultrasonic.
Weight solids (wt. %) of a material in suspension
[0183] The weight solids were determined by dividing the weight of the solid material by
the total weight of the aqueous suspension. The weight solids content was determined
at +160 °C using a Moisture Analyser MJ 33, Mettler Toledo.
Specific surface (BET) measurement
[0184] The specific surface area (in m
2/g) of the mineral filler was determined using the BET method, which is well known
to the skilled man (ISO 9277:1995). The total surface area (in m
2) of the mineral filler was then obtained by multiplication of the specific surface
area and the mass (in g) of the mineral filler. The method and the instrument are
known to the skilled person and are commonly used to determine specific surface of
fillers and pigments.
Specific charge (C/g)
[0185] The cationic polymer demand that is necessary to achieve a charge value of zero was
measured using the Mettler DL 77 titrator and the Mütec PCD-02 detector by means of
the cationic titration method. The cationic reagent was N/200 (0.005 N) methyl glycol
chitosan (chitosan), and the anionic reagent was N/400 (0.0025 N) K-polyvinyl-sulfate
(KPVS), both sold by WAKO Chemicals GmbH.
[0186] If necessary, the sample was adjusted to pH 8.0 +/- 0.1 with NaOH (0.1M) prior to
measurement.
[0187] Since experience showed that the first titration is not correct, 10 ml water were
first prepared in the detector followed by the addition of 0.5 ml KPVS. Afterwards,
titration with chitosan was made until it is back to shortly after the equivalence
point. Subsequently, the measurements were started. Between 0.5 and 2.0 ml of 0.005
molar reagent were used up during the titration to obtain reproducible values.
[0188] To avoid rapid sedimentation, the sample was drawn under stirring, by means of a
tared syringe. The content of the syringe was then rinsed into the sample vessel by
means of distilled water. Afterwards, the detector was filled with distilled water
up to the lower edge and the piston was inserted carefully. Subsequently, the cationic
titration solution was put on the memotitrator and the top of the burette was fixed
at the detector ensuring that it does not come into contact with the detector or the
liquid. After each titration, the development of the titration was verified with the
aid of the titration curve.
[0189] Calculation of the electrochemical charge:
wherein K = + 1 000
V: Consumption chitosan [ml]
c: Concentration chitosan [mol/l]
t: Titer factor chitosan
E: Weight-in quantity [g]
F: Mass fraction solids [g/g]
z: Valence (equivalence number)
[0190] The obtained charge value of µ Val/g was converted into C/g by multiplication with
the Faraday constant as follows:
Optical density
[0191] The optical density is a dimension for the thickness of the colour layer above the
substrate. Optical density values are calculated based on the spectral measurement,
therefore slight differences to the measurement with a densitometer may occur. The
calculation is made according to the DIN Norm 16536-2.
2. Examples
A. Suspensions comprising calcium carbonate-containing material
[0192] The details regarding the suspensions comprising calcium carbonate-containing material
as used in the example section are described in the following:
Suspension 1
[0193] A natural calcium carbonate (marble) of Italian origin is obtained by first autogenously
dry grinding 10 to 300 mm calcium carbonate rocks to a fineness corresponding to a
d50 value of between 42 to 48 µm, and subsequently wet grinding this dry-ground product
at +30 to +35°C in water in a 1.4-litre vertical attritor mill (Dynomill) at a weight
solids content of about 75 wt.-%, based on the total weight of the slurry, until 90
wt.-% of the particles have a diameter < 2 µm, 16 wt.-% have a diameter < 0.2 µm,
and a
d50 value of 0.9 µm was reached, using 0.82 wt.-% in respect to dry CaCO
3 of a comb polymer having a specific charge of -49 C/g measured at pH 5.9 and -69
C/g measured at pH 8 and an intrinsic viscosity of 30.3 ml/g (MelPers
® 2450, available from BASF, Germany). The charge density of the calcium carbonate-containing
material in the suspension was -0.3 C/g at pH 9. The specific surface (BET) was determined
to be 10.9 m
2/g.
Suspension 2
[0194] A natural calcium carbonate (marble) of Italian origin is obtained by first autogenously
dry grinding 10 to 300 mm calcium carbonate rocks to a fineness corresponding to a
d50 value of between 42 to 48 µm, and subsequently wet grinding this dry-ground product
at +30 to +35°C in water in a 1.4-litre vertical attritor mill (Dynomill) at a weight
solids content of about 75.9 wt.-%, based on the total weight of the slurry, until
90 wt.-% of the particles have a diameter < 2 µm, 12 wt.-% have a diameter < 0.2 µm,
and a
d50 value of 0.9 µm was reached, using 1.44 wt.-% in respect to dry CaCO
3 of a comb polymer having a specific charge of -92 C/g measured at pH 8 and an intrinsic
viscosity of 12.5 ml/g (MelPers
® 4343, available from BASF, Germany). The charge density of the calcium carbonate-containing
material in the suspension was -0.75 C/g at pH 9. The specific surface (BET) was determined
to be 10.5 m
2/g.
Suspension 3
[0195] A natural calcium carbonate (marble) of Italian origin is obtained by first autogenously
dry grinding 10 to 300 mm calcium carbonate rocks to a fineness corresponding to a
d50 value of between 42 to 48 µm, and subsequently wet grinding this dry-ground product
at +30 to +35°C in water in a 1.4-litre vertical attritor mill (Dynomill) at a weight
solids content of about 76 wt.-%, based on the total weight of the slurry, until 92
wt.-% of the particles have a diameter < 2 µm, 18 wt.-% have a diameter < 0.2 µm,
and a
d50 value of 0.75 µm was reached, using 1.1 wt.-% in respect to dry CaCO
3 of a comb polymer having a specific charge of -49 C/g measured at pH 5.9 and -69
C/g measured at pH 8 and an intrinsic viscosity of 30.3 ml/g (MelPers
® 2450, available from BASF, Germany). The charge density of the calcium carbonate-containing
material in the suspension was -0.4 C/g at pH 9. The conductivity of the suspension
was measured as being 510 µS/cm, while the pH of the suspension was 7.9 at +23 °C.
The specific surface (BET) was determined to be 11.9 m
2/g.
Example 1 (Comparative Example)
[0196] This example illustrates the prior art and concerns the processing of a suspension
comprising a calcium carbonate-containing material in combination with a solution
comprising a calcium salt of hydrochloric acid. In particular, the calcium carbonate-containing
material is added to the solution comprising a calcium salt of hydrochloric acid.
[0197] 30 g CaCl
2 (Fluka) were dissolved in 70 ml distilled water. The obtained solution had a pH of
8.6 at +23 °C. Into this solution, 30 g CaCO
3 (Fluka) were dispersed under agitation to form a suspension of CaCO
3 in CaCl
2 solution. The obtained suspension had a pH of 8.6 at +23 °C. Into this suspension
0.4 g Melpers 4343 (available from BASF, Germany), in form of a 50 wt.-% solution
(BASF), based on the total weight of the solution, corresponding to 0.66 wt.-% in
respect to CaCO
3 in the suspension, were dosed under agitation. The obtained suspension had a pH of
8.6 at +23 °C after 1 hour.
[0198] As can be gathered from the details regarding the measured pH, no pH drop to below
6 at +23 °C was observed.
Example 2 (Comparative Example)
[0199] This example illustrates the prior art and concerns the processing of a suspension
comprising a calcium carbonate-containing material in combination with a solution
comprising a calcium salt of hydrochloric acid. In particular, the calcium carbonate-containing
material is added to the solution comprising a calcium salt of hydrochloric acid.
[0200] 20 g CaCl
2 (Fluka) were dissolved in 60 ml distilled water in presence of 2.1 g Melpers 4343
(available from BASF, Germany), in form of a 50 wt.-% solution (BASF), based on the
total weight of the solution, and at a temperature of +50 °C. The obtained solution
had a pH of 7.7 at +23 °C. Into this solution, 100 g CaCO
3 (Fluka) were dispersed under agitation at about 35 °C to form a suspension of CaCO
3 in CaCl
2 solution. The obtained suspension had a pH of 7.3 at +23 °C after 1 hour.
[0201] As can be gathered from the details regarding the measured pH, no pH drop to below
6 at +23 °C was observed.
Example 3 (Inventive Example)
[0202] This example illustrates the invention and concerns the processing of a suspension
comprising a calcium carbonate-containing material with high dry matter content in
combination with hydrochloric acid as strong acid. In particular, the hydrochloric
acid is added to the calcium carbonate-containing material.
[0203] 598 g of the 75 wt.-% of suspension 1 was placed in a stirred 1 liter glass backer
and heated under agitation to +70 °C. To this suspension hydrochloric acid was added
drop wise as a 10 wt.-% solution. The goal was to add 164 g of the hydrochloric acid
solution in 45 minutes. The obtained aqueous suspension had solids content of 59.1
wt.-%, based on the total weight of the suspension.
[0204] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 1.
Table 1
|
-5 °C |
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
|
35 |
Brookfield viscosity after 1 day [mPas] |
65 |
|
pH after 1 hour |
|
5.4 |
pH after 1 day |
|
5.57 |
pH after 3 days |
|
5.58 |
pH after 6 days |
|
5.94 |
Conductivity after 6 days [mS/cm] |
42.1 |
53.0 |
[0205] From Table 1 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 4 (Inventive Example)
[0206] This example illustrates the invention and concerns the processing of a suspension
comprising calcium carbonate-containing material with high dry matter content in combination
with hydrochloric acid as strong acid. In particular, the hydrochloric acid is added
to the calcium carbonate-containing material.
[0207] 610 g of the 75.9 wt.-% of suspension 3 was placed in a stirred 1 liter glass backer
and heated under agitation to +75 °C.
[0208] To this suspension hydrochloric acid was added drop wise in form of a 10 wt.-% solution.
The goal was to add 164 g of the hydrochloric acid solution in 45 minutes. The obtained
aqueous suspension had solids content of 59.3 wt.-%, based on the total weight of
the suspension (suspension 4).
[0209] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 2.
Table 2
|
-5 °C |
+23 °C |
Brookfield viscosity after 6 day [mPas] |
65 |
70 |
pH after 1 hour |
|
5.13 |
pH after 2 days |
|
5.42 |
pH after 3 days |
|
5.41 |
pH after 6 days |
|
5.70 |
Conductivity after 6 days [mS/cm] |
44.9 |
53.0 |
[0210] From Table 2 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 5 (Inventive Example)
[0211] This example illustrates the invention and concerns the processing of a suspension
comprising calcium carbonate-containing material with high dry matter content in combination
with hydrochloric acid as strong acid. In particular, the hydrochloric acid is added
to the calcium carbonate-containing material.
[0212] 598 g of the 75 wt.-% of suspension 1 was placed in a stirred 1 liter glass backer
and heated under agitation to +80 °C. To this suspension hydrochloric acid was added
drop wise as a 37 wt.-% solution. The goal was to add 12.7 g of the hydrochloric acid
solution in 45 minutes. The obtained aqueous suspension had solids content of 67.4
wt.-%, based on the total weight of the suspension.
[0213] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 3.
Table 3
|
-5 °C |
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
|
60 |
Brookfield viscosity after 6 days [mPas] |
85 |
|
pH after 1 hour |
|
4.6 |
pH after 2 days |
|
4.78 |
pH after 6 days |
|
5.22 |
Conductivity after 6 days [mS/cm] |
89.7 |
80.0 |
[0214] From Table 3 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 6 (Inventive Example)
[0215] This example illustrates the invention and concerns the processing of a suspension
comprising calcium carbonate-containing material with high dry matter content in combination
with nitric acid as strong acid. In particular, the nitric acid is added to the calcium
carbonate-containing material.
[0216] 598 g of the 75 wt.-% of suspension 1 was placed in a stirred 1 liter glass backer
and heated under agitation to +60 °C. To this suspension nitric acid was added drop
wise as a 65 wt.-% solution. The goal was to add 46.8 g of the nitric acid solution
in 45 minutes. The obtained aqueous suspension had solids content of 74.4 wt.-%, based
on the total weight of the suspension.
[0217] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 4.
Table 4
|
-5 °C |
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
|
60 |
Brookfield viscosity after 6 day [mPas] |
125 |
|
pH after 1 hour |
|
5.7 |
pH after 1 day |
|
5.7 |
pH after 2 days |
|
5.79 |
Conductivity after 6 days [mS/cm] |
35.1 |
38.4 |
[0218] From Table 4 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 7 (Inventive Example)
[0219] This example illustrates the invention and concerns the processing of a suspension
comprising calcium carbonate-containing material with high dry matter content in combination
with hydrochloric acid as strong acid. In particular, the hydrochloric acid is added
to the calcium carbonate-containing material.
[0220] 1064 g of the 75 wt.-% of suspension 1 was placed in a stirred 1 liter glass backer
and agitated. The Brookfield viscosity of the suspension was 60 mPas measured at 100
rpm and +23 °C. To this suspension hydrochloric acid was added drop wise at 20 °C
as a 32 wt.-% solution. The goal was to add 182.5 g of the hydrochloric acid solution
in 45 minutes. The obtained aqueous suspension had solids content of 68.2 wt.-%, based
on the total weight of the suspension.
[0221] The Brookfield viscosity of the suspension was 60 mPas measured at 100 rpm and +23
°C, the pH at +23 °C was 4.45 measured 1 hour after the preparation of the suspension.
1 hour after the preparation of the suspension, the suspension was stored at +80 °C
for 6 hours and cooled back to +23 °C.
[0222] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 5.
Table 5
|
-10°C |
-5 °C |
+5 °C |
+23 °C |
Brookfield viscosity after 3 days [mPas] |
107 |
106 |
96 |
|
Brookfield viscosity after 6 days [mPas] |
|
80 |
|
|
pH after 1 day |
|
|
|
5.95 |
pH after 6 days |
|
|
|
5.18 |
Conductivity after 6 days [mS/cm] |
|
91.4 |
|
81.7 |
[0223] From Table 5 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 8 (Inventive Example)
[0224] This example illustrates the invention and concerns the processing of suspension
comprising calcium carbonate-containing material with high dry matter content in combination
with nitric acid as strong acid and a salt of a strong acid. In particular, the nitric
acid is added to the calcium carbonate-containing material.
[0225] 598 g of the 75 wt.-% of suspension 1 was placed in a stirred 1 liter glass backer
and heated under agitation to +70 °C. To this suspension nitric acid was added drop
wise as a 65 wt.-% solution. The goal was to add 46.8 g of the nitric acid solution
in 45 minutes. The obtained aqueous suspension was cooled to +20 °C and 23.4 g lithium
chloride was added to the suspension under agitation. The obtained aqueous suspension
had solids content of 75.9 wt.-%, based on the total weight of the suspension.
[0226] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 6.
Table 6
|
-6 °C |
-1 °C |
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
|
|
90 |
Brookfield viscosity after 1 day [mPas] |
152 |
|
93 |
Brookfield viscosity after 2 days [mPas] |
|
|
97 |
pH after 1 day |
|
5.5 |
5.6 |
Conductivity after 6 days [mS/cm] |
|
53.1 |
56.4 |
[0227] From Table 6 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 9 (Inventive Example)
[0228] This example illustrates the invention and concerns the processing of a suspension
comprising calcium carbonate containing material with high dry matter content in combination
with hydrochloric acid as strong acid and a medium strong acid. In particular, the
hydrochloric acid is added to the calcium carbonate-containing material.
[0229] 717 g of the 59.3 wt.-% of suspension 4, obtained in Example 4, were placed in a
500 ml glass flask. To this suspension phosphoric acid was slowly dosed under agitation
as 85 wt.-% solution at +23 °C over a period of 20 min. The obtained aqueous suspension
had solids content of 59.0 wt.-%, based on the total weight of the suspension (suspension
5).
[0230] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 7.
Table 7
|
-5 °C |
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
|
75 |
Brookfield viscosity after 4 days [mPas] |
62 |
65 |
pH after 1 hour |
|
4.8 |
pH after 1 day |
|
5.5 |
pH after 4 days |
5.97 |
5.7 |
pH after 3 weeks |
|
5.5 |
pH after 6 weeks |
|
5.4 |
Conductivity after 4 days [mS/cm] |
52.4 |
47.7 |
[0231] From Table 7 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material and a medium strong acid as additive
shows an unexpected drop of pH to below 6 compared to the prior art suspensions of
Examples 1 and 2 and features a low viscosity at -5 °C as well as a good stability
in acidic environment over more than 24 hours.
Example 10 (Inventive Example)
[0232] This example illustrates the invention and concerns the application of suspension
5, obtained in Example 9, as coating color in inkjet application.
[0233] A polyvinyl alcohol solution (1) was prepared by dissolving 3 g of PVA BP 05 A (Supplier,
Chang Chun Petrochemical Co., Ltd, 301 Songkiang Road, 7th Fl., Taipei, Taiwan, 10477)
in 15 g deionized water at +90°C in 20 minutes under agitation.
[0234] 100 g of the aqueous suspension 5, obtained in Example 9, were mixed under agitation
with 18 g of the PVA solution (1). The obtained coating color had solids content of
55 wt.-% based on the total weight of the coating color.
[0235] The obtained coating color was applied on 80 g/m
2 office paper "Centro Pro" hochweiss, holzfrei, matt (Art. No 105570, commercially
available from Inapa, Switzerland) in a range of different coat weights (using different
rods; rod 0 obtains a coat weight of 10.1 g/m
2, rod 1 obtains a coat weight of 12.1 g/m
2) by using a laboratory coater Typ Model 624 from Ericksen, 58675 Hemer, Germany.
The papers were dried for 10 min at +80 °C and conditioned before printing at +23
°C, 50 % rel. air humidity for 24 hour.
[0236] The coatings were tested at +23 °C and 50 % rel. air humidity by using a HP color
inkjet printer (HP Deskjet 1000, product No CH340B, model No J110a) for black and
color (HP Ink Cartridge 301 "black" CH561E and "tri-color" CH562E) on 4 x 4 cm squares
and Rod 0 to Rod 3.
[0237] The optical density of the test samples, i.e. coated with the inventive coating color,
was compared to non coated blank paper being a 80 g/m
2 office paper "Centro Pro" hochweiss, holzfrei, matt (Art. No 105570, commercially
available from Inapa, Switzerland). The details regarding the measured optical density
can be taken from Table 8.
Table 8
|
Prior art blank / no coating |
Invention Coat weight |
|
10.1 g/m2 |
12.1 g/m2 |
OD Black *** |
1.89 |
2.54 |
2.59 |
OD Blue *** |
1.13 |
1.44 |
1.45 |
*** Optical density Spectrolino™, Spectrophotometer, Handheld system |
[0238] From Table 8 it can be gathered that the coating of the raw paper with the coating
color comprising the inventive high solids aqueous suspension shows a clear improvement
in color density compared to the non-coated blank paper of the prior art.
Example 11 (Inventive Example)
[0239] This example illustrates the invention and concerns the processing of a suspension
comprising calcium carbonate-containing material with high dry matter content in combination
with hydrochloric acid as strong acid and aluminium hydroxide. In particular, the
hydrochloric acid is added to the calcium carbonate-containing material.
[0240] A suspension A was formed by dispersing 70 g Al(OH)
3 under agitation in 30 g of tap water. Furthermore, 2 g of a comb polymer having a
specific charge of -49 C/g measured at pH 5.9 and -69 C/g measured at pH 8 and an
intrinsic viscosity of 30.3 ml/g (MelPers
® 2450, available from BASF, Germany) was added. The pH of the suspension A at +23
°C after 1 hour of preparation was 8.4, the Brookfield viscosity after 1 hour and
24 hours of preparation was < 1 000 mPas measured at 100 rpm and +23 °C.
[0241] A suspension B was formed under agitation for 10 minutes by adding 14 g of AlCl
3 x 6 H
2O (Fluka, Switzerland Order No. 06232) to suspension A. The obtained aqueous suspension
had solids content of 70.1 wt.-%, based on the total weight of the suspension B.
[0242] The details regarding the measured Brookfield viscosities (determined at +23 °C and
100 rpm), pH at +23 °C and conductivity can be taken from Table 9.
Table 9
|
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
< 1 000 |
Brookfield viscosity after 1 day [mPas] |
< 1 000 |
pH after 10 min |
0.70 |
pH after 1 hour |
1.40 |
pH after 1 day |
1.67 |
Conductivity after 1 days [mS/cm] |
46.3 |
[0243] 100 g of the 59 wt.-% of suspension 5, obtained in Example 9, were placed in a 200
ml glass flask. To this aqueous suspension, 100 g of suspension B were slowly added
under agitation at +23 °C over a period of 60 min. The obtained aqueous suspension
had solids content of 62.9 wt.-%, based on the total weight of the suspension.
[0244] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity can be taken from Table 10.
Table 10
|
-5 °C |
+23 °C |
Brookfield viscosity after 1 hour [mPas] |
|
288 |
Brookfield viscosity after 6 hours [mPas] |
|
344 |
Brookfield viscosity after 10 days [mPas] |
< 700 |
< 700 |
pH after 1 hour |
|
4.2 |
pH after 6 hours |
|
4.6 |
pH after 10 days |
|
4.5 |
[0245] From Table 10 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material and aluminium hydroxide as additive
shows an unexpected drop of pH to below 6 compared to the prior art suspensions of
Examples 1 and 2 and features a low viscosity at -5 °C as well as a good stability
in acidic environment over more than 24 hours.
Example 12 (Inventive Example)
[0246] This example illustrates the invention and concerns the processing of a suspension
comprising a calcium carbonate-containing material with high dry matter content in
combination with a calcium salt of hydrochloric acid. In particular, the calcium salt
of hydrochloric acid is added to the calcium carbonate-containing material.
[0247] 315 g of the 76 wt.-% of suspension 3, having a pH of 7.9 at +23 °C, was placed in
a stirred 250 ml glass backer at +23 °C. To this suspension 31.7 g CaCl
2 x 2 H
2O were added under agitation in 5 minutes. The goal was to add in total 23.9 g of
the calcium salt of hydrochloric acid. The obtained aqueous suspension had solids
content of 75.5 wt.-%, based on the total weight of the suspension.
[0248] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity at +23 °C can be taken from Table
11.
Table 11
at Temp. of: |
-5 °C |
+23 °C |
Brookfield viscosity after 6 hour [mPas] |
45 |
45 |
pH after 1 hour |
|
4.6 |
pH after 1 day |
|
4.8 |
pH after 7 day |
|
4.9 |
Conductivity after 1 hour [mS/cm] |
|
64.6 |
[0249] From Table 11 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
[0250] In comparison reasons, 31.7 g CaCl
2 x 2 H
2O were dissolved in 75 g water under agitation. The goal was to have approximately
the same concentration of the calcium salt of hydrochloric acid as in the liquid phase
of the suspension of this example as described above. The details regarding the measured
pH at +23 °C and conductivity at +23 °C can be taken from Table 12
Table 12
at Temp. of: |
+23 °C |
pH after 1 hour |
9.4 |
pH after 7 day |
9.2 |
Conductivity after 1 hour [mS/cm] |
61.1 |
[0251] From the details set out in Table 11 versus Table 12, it can be gathered that totally
surprising the inventive high solids aqueous suspension comprising a calcium carbonate-containing
material has a stable acidic pH of far below 6 at +23 °C combining an alkaline suspension
of calcium carbonate having a pH of 8.4 with an alkaline solution of calcium salt
of hydrochloric acid having a pH of about 9.4 (as outlined in Table 12).
Example 13 (Inventive Example)
[0252] This example illustrates the invention and concerns the processing of a suspension
comprising a calcium carbonate-containing material with high dry matter content in
combination with a calcium salt of nitric acid. In particular, the calcium salt of
nitric acid is added to the calcium carbonate-containing material.
[0253] 500 g of the 76 wt.-% of suspension 3 was placed in a stirred 1 000 ml glass backer
at +23 °C. To this suspension 54 g Ca(NO
3)
2 x 4 H
2O were added under agitation in 5 minutes. The goal was to add in total 37.5 g of
the calcium salt of nitric acid. The obtained aqueous suspension had solids content
of 75.3 wt.-%, based on the total weight of the suspension.
[0254] The details regarding the measured Brookfield viscosities (determined at -5 °C and
+23 °C and 100 rpm), pH at +23 °C and conductivity at +23 °C can be taken from Table
13.
Table 13
at Temp. of: |
-5 °C |
+23 °C |
Brookfield viscosity after 6 hour [mPas] |
55 |
65 |
pH after 1 hour |
|
5.5 |
pH after 1 day |
|
5.8 |
Conductivity after 1 hour [mS/cm] |
|
34.6 |
[0255] From Table 13 it can be gathered that the inventive high solids aqueous suspension
comprising a calcium carbonate-containing material shows an unexpected drop of pH
to below 6 compared to the prior art suspensions of Examples 1 and 2 and features
a low viscosity at -5 °C as well as a good stability in acidic environment over more
than 24 hours.
Example 14 (inventive Example)
[0256] This example illustrates the invention and concerns the processing of a suspension
comprising a calcium carbonate in combination with a solution comprising a calcium
salt of hydrochloric acid. In particular, the calcium salt of hydrochloric acid is
added to the calcium carbonate-containing material.
[0257] 70 g CaCO
3 (Fluka) were dispersed under agitation in 70 ml distilled water to form a suspension
of CaCO
3. Into this suspension 1.5 g Melpers 4343 (available from BASF, Germany), in form
of a 50 wt.-% solution (BASF), based on the total weight of the solution, were added.
The obtained suspension had a pH of 7.5 at +23 °C. Into this suspension, 3 g CaCl
2 (Fluka) were dosed under agitation to form a CaCO
3 suspension comprising CaCl
2. Subsequently, further 4 g CaCl
2 (Fluka) were dosed under agitation into the suspension to form a CaCO
3 suspension comprising CaCl
2.
[0258] The details regarding the measured pH at +23 °C can be taken from Table 14.
Table 14
at Temp. of: |
+23 °C |
pH after 1 hour |
5.4 |
pH after 5 days |
5.9 |
[0259] As can be gathered from the details regarding the measured pH, an unexpected drop
of pH to below 6 at +23 °C was observed.
1. A high solids aqueous mineral and/or filler and/or pigment suspension in acidic pH
environment comprising:
a) at least one calcium carbonate-containing material comprising calcium carbonate-containing
particles, and
b) at least one salt of at least one strong acid, wherein the at least one strong
acid forming the at least one salt of at least one strong acid is selected from the
group consisting of acids having a pKa value of less than or equal to zero at +23 °C,
wherein the high solids aqueous suspension has
i) a solids content of at least 50 wt.-%, based on the total weight of the high solids
aqueous suspension,
ii) a Brookfield viscosity at 100 rpm of ≤ 1 000 mPas at a temperature of - 5 °C
iii) a pH of < 6 at +23 °C, and
iv) a conductivity of between 10 and 100 mS/cm at -5 °C and at +23 °C, and wherein
the high solids aqueous suspension comprises the at least one salt of at least one
strong acid in an amount of from 1 to 20 wt.-%, based on the total weight of the high
solids aqueous suspension.
2. The high solids aqueous mineral and/or filler and/or pigment suspension of claim 1,
wherein the calcium carbonate-containing particles of the at least one calcium carbonate-containing
material are selected from among natural calcium carbonate, precipitated calcium carbonate
or mixtures thereof.
3. The high solids aqueous mineral and/or filler and/or pigment suspension of claim 1
or 2, wherein the calcium carbonate-containing particles of the at least one calcium
carbonate-containing material have a weight median particle size d50 from 0.1 to 50 µm, preferably from 0.25 to 50 µm, more preferably from 0.3 to 5 µm,
and most preferably from 0.4 to 3 µm.
4. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the calcium carbonate-containing particles of the
at least one calcium carbonate-containing material have a specific surface area of
from 0.1 m2/g to 200 m2/g, preferably from 0.1 m2/g to 50 m2/g and more preferably from 0.1 m2/g to 20 m2/g, measured using nitrogen and the BET method.
5. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension comprises the
at least one calcium carbonate-containing material in an amount of at least 50 wt.-%,
preferably from 50 to 82 wt.-%, more preferably from 55 to 82 wt.-%, even more preferably
from 60 to 78 wt.-% and most preferably from 65 to 78 wt.-%, based on the total weight
of the high solids aqueous suspension.
6. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the at least one calcium carbonate-containing material
comprises at least one comb polymer, preferably the surface of the calcium carbonate-containing
particles of the at least one calcium carbonate-containing material are coated with
the at least one comb polymer.
7. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the at least one calcium carbonate-containing material
comprises at least one comb polymer having an intrinsic viscosity in the range of
5 to 99 ml/g, preferably in the range of 10 to 80 ml/g and most preferably in the
range of 10 to 50 ml/g.
8. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the at least one salt of at least one strong acid
comprises a divalent and/or trivalent cation, preferably the divalent cation is selected
from the group consisting of calcium, magnesium, strontium and mixtures thereof and/or
the trivalent cation preferably is aluminum.
9. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the at least one strong acid forming the at least
one salt of at least one strong acid is selected from the group consisting of hydrochloric
acid, nitric acid and mixtures thereof.
10. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension comprises at least
one comb polymer in an amount from 0.01 to 5 wt.-%, based on the total dry weight
of the calcium carbonate-containing material in the suspension, preferably from 0.05
to 4 wt.-%, more preferably from 0.1 to 3 wt.-%, even more preferably from 0.2 to
2 wt.-%, and most preferably from 0.25 to 1.5 wt.-% or from 0.5 to 1.25 wt.-%.
11. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension has solids content
from 50 to 82 wt.-%, preferably from 55 to 82 wt.-%, more preferably from 60 to 78
wt.-% and most preferably from 65 to 78 wt.-%, based on the total weight of the high
solids aqueous suspension.
12. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension has a Brookfield
viscosity at 100 rpm from 25 to 1 000 mPas at a temperature of -5 °C, preferably from
25 to 700 mPas at -5 °C, more preferably from 25 to 500 mPas at -5 °C and most preferably
from 50 to 300 mPas at -5 °C.
13. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension has a pH of between
4 and < 6 at +23 °C, preferably a pH of between 4.5 and < 6 at +23 °C and preferably
a pH of between 5 and < 6 at +23 °C.
14. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension has a conductivity
of between 20 mS/cm and 100 mS/cm measured at -5 °C and +23 °C and preferably between
30 mS/cm and 100 mS/cm measured at - 5 °C and +23 °C.
15. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension further comprises
at least one reaction product or products of the at least one calcium carbonate-containing
material with at least one medium strong acid and/or at least one reaction product
or products of the at least one calcium carbonate-containing material with at least
one weak acid.
16. The high solids aqueous mineral and/or filler and/or pigment suspension of claim 16,
wherein the at least one medium strong acid forming the at least one reaction product
or products of the at least one calcium carbonate-containing material is selected
from the group consisting of acids having a pKa value of between 0 and 2.5 at +23 °C, preferably the at least one medium strong acid
is selected from H2SO3, HSO4-, H3PO4, oxalic acid and mixtures thereof and/or the at least one weak acid forming the at
least one reaction product or products of the at least one calcium carbonate-containing
material is selected from the group consisting of acids having a pKa value of between >2.5 and 6 at +23 °C, preferably the at least one weak acid is selected
from citric acid, tartaric acid and mixtures thereof.
17. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the molar quantity of the sum, expressed by the generated
H3O+ ions, of the at least one medium strong acid forming the at least one reaction product
or products of the at least one calcium carbonate-containing material and/or the at
least one weak acid forming the at least one reaction product or products of the at
least one calcium carbonate-containing material and the at least one strong acid forming
the at least one salt of at least one strong acid relative to the quantity of moles
of CaCO3 is in total between 0.01 and 1.9.
18. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension further comprises
aluminum hydroxide and/or magnesium hydroxide.
19. The high solids aqueous mineral and/or filler and/or pigment suspension of any one
of the preceding claims, wherein the high solids aqueous suspension has a positive
charge density at pH 5, preferably of at least +0.1 C/g at pH 5, more preferably of
at least +0.5 C/g at pH 5, even more preferably of at least +1 C/g at pH 5 and most
preferably of at least +1.5 C/g at pH 5.
20. A method for producing a high solids aqueous mineral and/or filler and/or pigment
suspension as defined in any one of claims 1 to 19, comprising the steps of
a) providing an aqueous suspension comprising at least one calcium carbonate-containing
material, as defined in any one of claims 1 to 7, wherein the calcium carbonate-containing
material has a charge density of between +2 and -2 C/g at pH 9, ,
b) providing
i) at least one strong acid selected from the group consisting of acids having a pKa value of less than or equal to zero at +23 °C as defined in any one of claims 1 or
9, and/or
ii) at least one salt of at least one strong acid, wherein the at least one strong
acid forming the at least one salt of at least one strong acid is selected from the
group consisting of acids having a pKa value of less than or equal to zero at +23 °C as defined in any one of claims 1,
8 or 9,
c) adding the at least one strong acid and/or the at least one salt of at least one
strong acid of step b) to the aqueous suspension comprising at least one calcium carbonate-containing
material of step a),
d) optionally grinding the aqueous suspension comprising at least one calcium carbonate-containing
material of step a) before and/or during and/or after step c),
wherein the high solids aqueous suspension after step c) and/or d) has
i) a solids content of at least 50 wt.-%, based on the total weight of the high solids
aqueous suspension,
ii) a Brookfield viscosity at 100 rpm of ≤ 1 000 mPas at a temperature of -5 °C,
iii) a pH of < 6 at +23 °C, and
iv) a conductivity of between 10 and 100 mS/cm at -5 °C and at +23 °C, and wherein
the high solids aqueous suspension comprises the at least one salt of at least one
strong acid in an amount of from 1 to 20 wt.-%, based on the total weight of the high
solids aqueous suspension.
21. The method of claim 20, wherein the method further comprises step e) of providing
at least one medium strong acid selected from the group consisting of acids having
a pKa value of between 0 and 2.5 at +23 °C, preferably the at least one medium strong acid
is selected from H2SO3, HSO4-, H3PO4, oxalic acid and mixtures thereof, and/or at least one weak acid selected from the
group consisting of acids having a pKa value of between >2.5 to 6.0 at +23 °C, preferably the at least one weak acid is
selected from citric acid and/or tartaric acid.
22. The method of claim 21, wherein the method further comprises step f) of contacting
the aqueous suspension comprising at least one calcium carbonate-containing material
of step a) with the at least one medium strong acid and/or at least one weak acid
of step e) during and/or after step c), and/or during and/or after optional step d).
23. The method of any one of claims 20 to 22, wherein step c) and/or step d) and/or step
f) is carried out at a temperature of between +5 °C and +99 °C, preferably between
+20 °C and +85 °C and most preferably between +20 °C and +50 °C and most preferably
between +50 °C and +85 °C.
24. The method of any one of claims 20 to 23, wherein the method further comprises step
g) of concentrating the obtained high solids aqueous mineral and/or filler and/or
pigment suspension.
25. The method of any one of claims 20 to 24, wherein the method further comprises drying
the obtained high solids aqueous mineral and/or filler and/or pigment suspension.
26. Calcium carbonate-containing material obtainable by drying the high solids aqueous
mineral and/or filler and/or pigment suspension of any one of claims 1 to 19.
27. Use of the high solids aqueous mineral and/or filler and/or pigment suspension of
any one of claims 1 to 19 and/or the calcium carbonate-containing material of claim
26 in paper making, paper coating, plastic, agricultural and/or paint applications.
28. Use of the high solids aqueous mineral and/or filler and/or pigment suspension of
any one of claims 1 to 19 and/or the calcium carbonate-containing material of claim
26 as filler in paper.
29. The use of claim 27, wherein the high solids aqueous mineral and/or filler and/or
pigment suspension and/or the calcium carbonate-containing material is used as a support
for digital printing, preferred ink jet printing, or for flexo, rotogravure and/or
offset printing, most preferably for black ink printing in inkjet printing.
30. A coating color formulation comprising the high solids aqueous mineral and/or filler
and/or pigment suspension of any one of claims 1 to 19 and/or the calcium carbonate-containing
material of claim 26 and a natural and/or synthetic binder, the binder preferably
consisting of styrene-butadiene, styrene-acrylate, polyvinyl acetate, polyvinyl alcohol,
starch or mixtures thereof, and most preferably the binder contains or consists of
polyvinyl alcohol.
1. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
und in einer Umgebung mit saurem pH, umfassend:
a) wenigstens ein Calciumcarbonat enthaltendes Material, das Calciumcarbonat enthaltende
Partikel umfasst, und
b) wenigstens ein Salz von wenigstens einer starken Säure, wobei die wenigstens eine
starke Säure, die das wenigstens eine Salz von wenigstens einer starken Säure bildet,
ausgewählt ist aus der Gruppe bestehend aus Säuren mit einem pKa-Wert kleiner oder gleich 0 bei +23°C,
wobei die wässrige Suspension mit einem hohen Feststoffgehalt aufweist:
i) einen Feststoffgehalt von wenigstens 50 Gew.-%, bezogen auf das Gesamtgewicht der
wässrigen Suspension mit einem hohen Feststoffgehalt,
ii) eine Brookfield-Viskosität bei 100 U/min von ≤ 1 000 mPa·s bei einer Temperatur
von -5°C,
iii) einen pH von < 6 bei +23°C, und
iv) eine Leitfähigkeit zwischen 10 und 100 mS/cm bei -5°C und bei +23°C, und
wobei die wässrige Suspension mit einem hohen Feststoffgehalt das wenigstens eine
Salz von wenigstens einer starken Säure in einer Menge von 1 bis 20 Gew.-% umfasst,
bezogen auf das Gesamtgewicht der wässrigen Suspension mit einem hohen Feststoffgehalt.
2. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach Anspruch 1, bei der die Calciumcarbonat enthaltenden Partikel des wenigstens
einen Calciumcarbonat enthaltenden Materials ausgewählt sind aus natürlichem Calciumcarbonat,
gefälltem Calciumcarbonat, oder Gemischen davon.
3. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach Anspruch 1 oder 2, bei der die Calciumcarbonat enthaltenden Partikel des wenigstens
einen Calciumcarbonat enthaltenden Materials eine gewichtsgemittelte Partikelgrösse
d50 von 0,1 bis 50 µm aufweisen, bevorzugt von 0,25 bis 50 µm, bevorzugter von 0,3 bis
5 µm, und am meisten bevorzugt von 0,4 bis 3 µm.
4. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die Calciumcarbonat enthaltenden
Partikel des wenigstens einen Calciumcarbonat enthaltenden Materials eine spezifische
Oberfläche von 0,1 m2/g bis 200 m2/g aufweisen, bevorzugt von 0,1 m2/g bis 50 m2/g, und bevorzugter von 0,1 m2/g bis 20 m2/g, gemessen durch Verwenden von Stickstoff und dem BET-Verfahren.
5. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt das wenigstens eine Calciumcarbonat enthaltende Material in
einer Menge von wenigstens 50 Gew.-% umfasst, bevorzugt von 50 bis 82 Gew.-%, bevorzugter
von 55 bis 82 Gew.-%, noch bevorzugter von 60 bis 78 Gew.-%, und am meisten bevorzugt
von 65 bis 78 Gew.-%, bezogen auf das Gesamtgewicht der wässrigen Suspension mit einem
hohen Feststoffgehalt.
6. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der das wenigstens eine Calciumcarbonat
enthaltende Material wenigstens ein Kammpolymer umfasst, bevorzugt ist die Oberfläche
der Calciumcarbonat enthaltenden Partikel des wenigstens einen Calciumcarbonat enthaltenden
Materials mit dem wenigstens einen Kammpolymer beschichtet.
7. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der das wenigstens eine Calciumcarbonat
enthaltende Material wenigstens ein Kammpolymer mit einer intrinsischen Viskosität
im Bereich von 5 bis 99 ml/g umfasst, bevorzugt im Bereich von 10 bis 80 ml/g, und
am meisten bevorzugt im Bereich von 10 bis 50 ml/g.
8. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der das wenigstens eine Salz von wenigstens
einer starken Säure ein divalentes und/oder trivalentes Kation umfasst, bevorzugt
ist das divalente Kation ausgewählt aus der Gruppe bestehend aus Calcium, Magnesium,
Strontium und Gemischen davon, und/oder das trivalente Kation ist bevorzugt Aluminium.
9. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wenigstens eine starke Säure,
die das wenigstens eine Salz von wenigstens einer starken Säure bildet, ausgewählt
ist aus der Gruppe bestehend aus Salzsäure, Salpetersäure und Gemischen davon.
10. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt wenigstens ein Kammpolymer in einer Menge von 0,01 bis 5 Gew.-%
umfasst, bezogen auf das Gesamttrockengewicht des Calciumcarbonat enthaltenden Materials
in der Suspension, bevorzugt von 0,05 bis 4 Gew.-%, bevorzugter von 0,1 bis 3 Gew.-%,
noch bevorzugter von 0,2 bis 2 Gew.-%, und am meisten bevorzugt von 0,25 bis 1,5 Gew.-%,
oder von 0,5 bis 1,25 Gew.-%.
11. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt einen Feststoffgehalt von 50 bis 82 Gew.-% aufweist, bevorzugt
von 55 bis 82 Gew.-%, bevorzugter von 60 bis 78 Gew.-%, und am meisten bevorzugt von
65 bis 78 Gew.-%, bezogen auf das Gesamtgewicht der wässrigen Suspension mit einem
hohen Feststoffgehalt.
12. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt eine Brookfield-Viskosität bei 100 U/min von 25 bis 1 000 mPa·s
bei einer Temperatur von -5°C aufweist, bevorzugt von 25 bis 700 mPa·bei -5°C, bevorzugter
von 25 bis 500 mPa·s bei -5°C, und am meisten bevorzugt von 50 bis 300 mPa·s bei -5°C.
13. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt einen pH zwischen 4 und < 6 bei +23°C aufweist, bevorzugt einen
pH zwischen 4,5 und < 6 bei +23°C, und bevorzugt einen pH zwischen 5 und < 6 bei +23°C.
14. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt eine Leitfähigkeit zwischen 20 mS/cm und 100 mS/cm, gemessen
bei -5°C und bei +23°C, aufweist, und bevorzugt zwischen 30 mS/cm und 100 mS/cm, gemessen
bei - 5°C und bei +23°C.
15. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt ferner wenigstens ein Reaktionsprodukt oder Reaktionsprodukte
des wenigstens einen Calciumcarbonat enthaltenden Materials mit wenigstens einer mittelstarken
Säure umfasst, und/oder wenigstens ein Reaktionsprodukt oder Reaktionsprodukte des
wenigstens einen Calciumcarbonat enthaltenden Materials mit wenigstens einer schwachen
Säure.
16. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wenigstens eine mittelstarke
Säure, die das wenigstens eine Reaktionsprodukt oder Reaktionsprodukte des wenigstens
einen Calciumcarbonat enthaltenden Materials bildet, ausgewählt ist aus der Gruppe
bestehend aus Säuren mit einem pKa-Wert zwischen 0 und 2,5 bei +23°C, bevorzugt ist die wenigstens eine mittelstarke
Säure ausgewählt aus H2SO3, HSO4-, H3PO4, Oxalsäure und Gemischen davon, und/oder die wenigstens eine schwache Säure, die
wenigstens ein Reaktionsprodukt oder Reaktionsprodukte des wenigstens einen Calciumcarbonat
enthaltenden Materials bildet, ist ausgewählt aus der Gruppe bestehend aus Säuren
mit einem pKa-Wert zwischen > 2,5 und 6 bei +23°C, bevorzugt ist die wenigstens eine schwache Säure
ausgewählt aus Zitronensäure, Weinsäure und Gemischen davon.
17. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die Summe der Molmenge, ausgedrückt
durch die erzeugten H3O+-Ionen, der wenigstens einen mittelstarken Säure, die das wenigstens eine Reaktionsprodukt
oder Reaktionsprodukte des wenigstens einen Calciumcarbonat enthaltenden Materials
bildet, und/oder der wenigstens einen schwachen Säure, die das wenigstens eine Reaktionsprodukt
oder Reaktionsprodukte des wenigstens einen Calciumcarbonat enthaltenden Materials
bildet, und der wenigstens einen starken Säure, die das wenigstens eine Salz von wenigstens
einen starken Säure bildet, bezüglich der Molmenge an CaCO3, insgesamt zwischen 0,01 und 1,9 beträgt.
18. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt ferner Aluminiumhydroxid und/oder Magnesiumhydroxid umfasst.
19. Wässrige Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt
nach einem der vorhergehenden Ansprüche, bei der die wässrige Suspension mit einem
hohen Feststoffgehalt eine positive Ladungsdichte bei pH 5 aufweist, bevorzugt von
wenigstens +0,1 C/g bei pH 5, bevorzugter von wenigstens +0,5 C/g bei pH 5, noch bevorzugter
von wenigstens +1 C/g bei pH 5, und am meisten bevorzugt von wenigstens +1,5 C/g bei
pH 5.
20. Verfahren zur Herstellung einer wässrigen Mineral- und/oder Füllstoff- und/oder Pigmentsuspension
mit einem hohen Feststoffgehalt, wie in einem der Ansprüche 1 bis 19 definiert, umfassend
die Schritte:
a) Bereitstellen von einer wässrigen Suspension, die wenigstens ein Calciumcarbonat
enthaltendes Material umfasst, wie in einem der Ansprüche 1 bis 7 definiert, bei der
das Calciumcarbonat enthaltende Material eine Ladungsdichte zwischen +2 und -2 C/g
bei pH 9 aufweist,
b) Bereitstellen von
i) wenigstens einer starken Säure, ausgewählt aus der Gruppe bestehend aus Säuren
mit einem pKa-Wert kleiner oder gleich 0 bei +23°C, wie in einem der Ansprüche 1 oder 9 definiert,
und/oder
ii) wenigstens einem Salz von wenigstens einer starken Säure, wobei die wenigstens
eine starke Säure, die das wenigstens eine Salz von wenigstens einer starken Säure
bildet, ausgewählt ist aus der Gruppe bestehend aus Säuren mit einem pKa-Wert kleiner oder gleich 0 bei +23°C, wie in einem der Ansprüche 1, 8 oder 9 definiert,
c) Zugeben der wenigstens einen starken Säure und/oder des wenigstens einen Salzes
von wenigstens einer starken Säure aus Schritt b) zu der wässrigen Suspension, die
wenigstens ein Calciumcarbonat enthaltendes Material umfasst, aus Schritt a),
d) gegebenenfalls Vermahlen der wässrigen Suspension, die wenigstens ein Calciumcarbonat
enthaltendes Material umfasst, aus Schritt a) vor und/oder während und/oder nach Schritt
c),
wobei die wässrige Suspension mit einem hohen Feststoffgehalt nach Schritt c) und/oder
d)
i) einen Feststoffgehalt von wenigstens 50 Gew.-% aufweist, bezogen auf das Gesamtgewicht
der wässrigen Suspension mit einem hohen Feststoffgehalt,
ii) eine Brookfield-Viskosität bei 100 U/min von ≤ 1 000 mPa·s bei einer Temperatur
von -5°C aufweist,
iii) einen pH von < 6 bei +23°C aufweist, und
iv) eine Leitfähigkeit zwischen 10 und 100 mS/cm bei -5°C und bei +23°C aufweist,
und
wobei die wässrige Suspension mit einem hohen Feststoffgehalt das wenigstens eine
Salz von wenigstens einer starken Säure in einer Menge von 1 bis 20 Gew.-% umfasst,
bezogen auf das Gesamtgewicht der wässrigen Suspension mit einem hohen Feststoffgehalt.
21. Verfahren nach Anspruch 20, wobei das Verfahren ferner Schritt e) umfasst, bei dem
wenigstens eine mittelstarke Säure bereitgestellt wird, ausgewählt aus der Gruppe
bestehend aus Säuren mit einem pKa-Wert zwischen 0 und 2,5 bei +23°C, bevorzugt ist die wenigstens eine mittelstarke
Säure ausgewählt aus H2SO3, HSO4-, H3PO4, Oxalsäure und Gemischen davon, und/oder wenigstens eine schwache Säure, ausgewählt
aus der Gruppe bestehend aus Säuren mit einem pKa-Wert zwischen > 2,5 und 6,0 bei +23°C, bevorzugt ist die wenigstens eine schwache
Säure ausgewählt aus Zitronensäure und/oder Weinsäure.
22. Verfahren nach Anspruch 21, wobei das Verfahren ferner Schritt f) umfasst, bei dem
die wässrige Suspension, die wenigstens ein Calciumcarbonat enthaltendes Material
umfasst, aus Schritt a) mit der wenigstens einen mittelstarken Säure und/oder wenigstens
einen schwachen Säure aus Schritt e) während und/oder nach Schritt c), und/oder während
und/oder nach dem optionalen Schritt d) in Kontakt gebracht wird.
23. Verfahren nach einem der Ansprüche 20 bis 22, bei dem Schritt c) und/oder Schritt
d) und/oder Schritt f) bei einer Temperatur zwischen +5°C und +99°C ausgeführt wird
bzw. werden, bevorzugt zwischen +20°C und +85°C, und am meisten bevorzugt zwischen
+20°C und +50°C, und am meisten bevorzugt zwischen +50°C und +85°C.
24. Verfahren nach einem der Ansprüche 20 bis 23, wobei das Verfahren ferner Schritt g)
umfasst, bei dem die erhaltene wässrigen Mineral- und/oder Füllstoff- und/oder Pigmentsuspension
mit einem hohen Feststoffgehalt konzentriert wird.
25. Verfahren nach einem der Ansprüche 20 bis 24, wobei das Verfahren ferner das Trocknen
der erhalten wässrigen Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit
einem hohen Feststoffgehalt umfasst.
26. Calciumcarbonat enthaltendes Material, erhältlich durch Trocknen der wässrigen Mineral-
und/oder Füllstoff- und/oder Pigmentsuspension mit einem hohen Feststoffgehalt gemäss
einem der Ansprüche 1 bis 19.
27. Verwendung der wässrigen Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit
einem hohen Feststoffgehalt gemäss einem der Ansprüche 1 bis 19 und/oder des Calciumcarbonat
enthaltenden Materials gemäss Anspruch 26 in Papierherstellungs-, Papierbeschichtungs-,
Kunststoff-, Agrarindustrie- und/oder Farbanwendungen.
28. Verwendung der wässrigen Mineral- und/oder Füllstoff- und/oder Pigmentsuspension mit
einem hohen Feststoffgehalt gemäss einem der Ansprüche 1 bis 19 und/oder des Calciumcarbonat
enthaltenden Materials gemäss Anspruch 26 als Füllstoff in Papier.
29. Verwendung nach Anspruch 27, bei der die wässrige Mineral- und/oder Füllstoff- und/oder
Pigmentsuspension mit einem hohen Feststoffgehalt und/oder das Calciumcarbonat enthaltende
Material als ein Träger für Digitaldruck verwendet wird, bevorzugt Tintenstrahldruck,
oder für Flexodruck, Tiefdruck- und/oder Offsetdruck, am meisten bevorzugt für Tintenstrahldruck
mit schwarzer Tinte.
30. Streichfarbformulierung, umfassend die wässrige Mineral- und/oder Füllstoff- und/oder
Pigmentsuspension mit einem hohen Feststoffgehalt gemäss einem der Ansprüche 1 bis
19 und/oder das Calciumcarbonat enthaltende Material gemäss Anspruch 26 und ein natürliches
und/oder synthetisches Bindemittel, wobei das Bindemittel bevorzugt besteht aus Styrol-Butadien,
Styrol-Acrylat, Polyvinylacetat, Polyvinylalkohol, Stärke oder Gemischen davon, und
am meisten bevorzugt enthält oder besteht das Bindemittel aus Polyvinylalkohol.
1. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides dans un
environnement à pH acide comprenant :
a) au moins une substance contenant du carbonate de calcium comprenant des particules
contenant du carbonate de calcium, et
b) au moins un sel d'au moins un acide fort, l'acide fort formant le sel d'au moins
un acide fort étant choisi dans le groupe constitué par les acides ayant une valeur
de pKa inférieure ou égale à zéro à +23 °C,
la suspension aqueuse riche en solides ayant
i) une teneur en solides d'au moins 50 % en poids, par rapport au poids total de la
suspension aqueuse riche en solides,
ii) une viscosité de Brookfield à 100 tr/min ≤ 1000 mPas à une température de -5 °C,
iii) un pH < 6 à +23 °C, et
iv) une conductivité comprise entre 10 et 100 mS/cm à -5 °C et à +23 °C, et
la suspension aqueuse riche en solides comprenant le sel d'au moins un acide fort
en une quantité de 1 à 20 % en poids, par rapport au poids total de la suspension
aqueuse riche en solides.
2. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon la
revendication 1, dans laquelle les particules contenant du carbonate de calcium de
la substance contenant du carbonate de calcium sont choisies parmi le carbonate de
calcium naturel, le carbonate de calcium précipité ou des mélanges de ceux-ci.
3. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon la
revendication 1 ou 2, dans laquelle les particules contenant du carbonate de calcium
de la substance contenant du carbonate de calcium ont une granulométrie moyenne en
poids d50 de 0,1 à 50 µm, de préférence de 0,25 à 50 µm, plus préférablement de 0,3 à 5 µm,
et de manière préférée entre toutes de 0,4 à 3 µm.
4. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle les particules contenant
du carbonate de calcium de la substance contenant du carbonate de calcium ont une
surface spécifique de 0,1 m2/g à 200 m2/g, de préférence de 0,1 m2/g à 50 m2/g et plus préférablement de 0,1 m2/g à 20 m2/g, mesurée selon la méthode BET et en utilisant de l'azote.
5. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides comprend la substance contenant du carbonate de calcium en une quantité
d'au moins 50 % en poids, de préférence de 50 à 82 % en poids, plus préférablement
de 55 à 82 % en poids, encore plus préférablement de 60 à 78 % en poids et de manière
préférée entre toutes de 65 à 78 % en poids, par rapport au poids total de la suspension
aqueuse riche en solides.
6. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la substance contenant du
carbonate de calcium comprend au moins un polymère en peigne, de préférence, la surface
des particules contenant du carbonate de calcium de la substance contenant du carbonate
de calcium est revêtue avec le polymère en peigne.
7. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la substance contenant du
carbonate de calcium comprend un polymère en peigne ayant une viscosité intrinsèque
comprise dans la plage allant de 5 à 99 ml/g, de préférence dans la plage allant de
10 à 80 ml/g et de manière préférée entre toutes dans la plage allant de 10 à 50 ml/g.
8. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle le sel d'au moins un acide
fort comprend un cation divalent et/ou trivalent, de préférence le cation divalent
est choisi dans le groupe constitué par le calcium, le magnésium, le strontium et
des mélanges de ceux-ci et/ou le cation trivalent est de préférence l'aluminium.
9. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle l'acide fort formant le sel
d'au moins un acide fort est choisi dans le groupe constitué par l'acide chlorhydrique,
l'acide nitrique et des mélanges de ceux-ci.
10. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides comprend au moins un polymère en peigne en une quantité de 0,01 à 5 % en
poids, par rapport au poids total sec de la substance contenant du carbonate de calcium
dans la suspension, de préférence de 0,05 à 4 % en poids, plus préférablement de 0,1
à 3 % en poids, encore plus préférablement de 0,2 à 2 % en poids, et de manière préférée
entre toutes de 0,25 à 1,5 % en poids ou de 0,5 à 1,25 % en poids.
11. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides a une teneur en solides de 50 à 82 % en poids, de préférence de 55 à 82
% en poids, plus préférablement de 60 à 78 % en poids et de manière préférée entre
toutes de 65 à 78 % en poids, par rapport au poids total de la suspension aqueuse
riche en solides.
12. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides a une viscosité de Brookfield à 100 tr/min de 25 à 1000 mPas à une température
de -5 °C, de préférence de 25 à 700 mPas à -5 °C, plus préférablement de 25 à 500
mPas à -5 °C et de manière préférée entre toutes de 50 à 300 mPas à -5 °C.
13. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides a un pH compris entre 4 et < 6 à +23 °C, de préférence un pH compris entre
4,5 et < 6 à +23 °C et de préférence un pH compris entre 5 et < 6 à +23 °C.
14. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides a une conductivité comprise entre 20 mS/cm et 100 mS/cm mesurée à -5 °C
et +23 °C et de préférence comprise entre 30 mS/cm et 100 mS/cm mesurée à -5 °C et
+23 °C.
15. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides comprend en outre au moins un produit réactionnel de la substance contenant
du carbonate de calcium avec au moins un acide moyennement fort et/ou au moins un
produit réactionnel de la substance contenant du carbonate de calcium avec au moins
un acide faible.
16. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon la
revendication 16, dans laquelle l'acide moyennement fort formant le ou les produits
réactionnels de la substance contenant du carbonate de calcium est choisi dans le
groupe constitué par les acides ayant une valeur de pKa comprise entre 0 et 2,5 à +23 °C, de préférence l'acide moyennement fort est choisi
parmi H2SO3, HSO4-, H3PO4, l'acide oxalique et des mélanges de ceux-ci et/ou l'acide faible formant le ou les
produits réactionnels de la substance contenant du carbonate de calcium est choisi
dans le groupe constitué par les acides ayant une valeur de pKa comprise entre >2,5 et 6 à +23 °C, de préférence l'acide faible est choisi parmi
l'acide citrique, l'acide tartrique et des mélanges de ceux-ci.
17. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la quantité molaire de la
somme, exprimée par les ions H3O+ générés, de l'acide moyennement fort formant le ou les produits réactionnels de la
substance contenant du carbonate de calcium et/ou de l'acide faible formant le ou
les produits réactionnels de la substance contenant du carbonate de calcium et de
l'acide fort formant le sel d'au moins un acide fort par rapport à la quantité molaire
de CaCO3 est comprise entre 0,01 et 1,9 au total.
18. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides comprend en outre de l'hydroxyde d'aluminium et/ou de l'hydroxyde de magnésium.
19. Suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications précédentes, dans laquelle la suspension aqueuse riche
en solides a une densité de charge positive à pH 5, de préférence d'au moins +0,1
C/g à pH 5, plus préférablement d'au moins +0,5 C/g à pH 5, encore plus préférablement
d'au moins +1 C/g à pH 5 et de manière préférée entre toutes d'au moins +1,5 C/g à
pH 5.
20. Procédé de production d'une suspension aqueuse de minéral et/ou charge et/ou pigment
riche en solides selon l'une quelconque des revendications 1 à 19, comprenant les
étapes consistant à
a) fournir une suspension aqueuse comprenant au moins une substance contenant du carbonate
de calcium, tel que définie selon l'une quelconque des revendications 1 à 7, la substance
contenant du carbonate de calcium ayant une densité de charge comprise entre +2 et
-2 C/g à pH 9
b) fournir
i) au moins un acide fort choisi dans le groupe constitué par les acides ayant une
valeur de pKa inférieure ou égale à zéro à +23 °C tel que défini selon l'une quelconque des revendications
1 ou 9, et/ou
ii) au moins un sel d'un acide fort, l'acide fort formant le sel d'au moins un acide
fort étant choisi dans le groupe constitué par les acides ayant une valeur de pKa inférieure ou égale à zéro à +23 °C tel que défini selon l'une quelconque des revendications
1, 8 ou 9,
c) ajouter l'acide fort et/ou le sel d'au moins un acide fort de l'étape b) à la suspension
aqueuse comprenant au moins une substance contenant du carbonate de calcium de l'étape
a),
d) broyer facultativement la suspension aqueuse comprenant au moins une substance
contenant du carbonate de calcium de l'étape a) avant et/ou pendant et/ou après l'étape
c),
la suspension aqueuse riche en solides après l'étape c) et/ou d) ayant
i) une teneur en solides d'au moins 50 % en poids, par rapport au poids total de la
suspension aqueuse riche en solides,
ii) une viscosité de Brookfield à 100 tr/min ≤ 1000 mPas à une température de -5 °C,
iii) un pH < 6 à +23 °C, et
iv) une conductivité comprise entre 10 et 100 mS/cm à -5 °C et à +23 °C, et
la suspension aqueuse riche en solides comprenant le sel d'au moins un acide fort
en une quantité de 1 à 20 % en poids, par rapport au poids total de la suspension
aqueuse riche en solides.
21. Procédé selon la revendication 20, le procédé comprenant en outre l'étape e) consistant
à fournir au moins un acide moyennement fort choisi dans le groupe constitué par les
acides ayant une valeur de pKa comprise entre 0 et 2,5 à +23 °C, de préférence l'acide moyennement fort est choisi
parmi H2SO3, HSO4-, H3PO4, l'acide oxalique et des mélanges de ceux-ci et/ou au moins un acide faible choisi
dans le groupe constitué par les acides ayant une valeur de pKa comprise entre >2,5 et 6 à +23 °C, de préférence l'acide faible est choisi est choisi
parmi l'acide citrique et/ou l'acide tartrique.
22. Procédé selon la revendication 21, le procédé comprenant en outre l'étape f) consistant
à mettre en contact la suspension aqueuse comprenant au moins une substance contenant
du carbonate de calcium de l'étape a) avec au moins un acide moyennement fort et/ou
au moins un acide faible de l'étape e) pendant et/ou après l'étape c), et/ou pendant
et/ou après l'étape d) facultative.
23. Procédé selon l'une quelconque des revendications 20 à 22, dans lequel l'étape c)
et/ou l'étape d) et/ou l'étape f) est réalisée à une température comprise entre +5
°C et +99 °C, de préférence comprise entre +20 °C et +85 °C et de manière préférée
entre toutes comprise entre +20 °C et +50 °C et de manière préférée entre toutes comprise
entre +50 °C et +85 °C.
24. Procédé selon l'une quelconque des revendications 20 à 23, le procédé comprenant en
outre l'étape g) consistant à concentrer la suspension aqueuse de minéral et/ou charge
et/ou pigment riche en solides obtenue.
25. Procédé selon l'une quelconque des revendications 20 à 24, le procédé consistant en
outre à sécher la suspension aqueuse de minéral et/ou charge et/ou pigment riche en
solides.
26. Substance contenant du carbonate de calcium pouvant être obtenue par séchage de la
suspension aqueuse de minéral et/ou charge et/ou pigment riche en solides selon l'une
quelconque des revendications 1 à 19.
27. Utilisation de la suspension aqueuse de minéral et/ou charge et/ou pigment riche en
solides selon l'une quelconque des revendications 1 à 19 et/ou de la substance contenant
du carbonate de calcium selon la revendication 26 dans la fabrication de papier, le
couchage du papier, les plastiques, les applications agricoles et/ou de peinture.
28. Utilisation de la suspension aqueuse de minéral et/ou charge et/ou pigment riche en
solides selon l'une quelconque des revendications 1 à 19 et/ou de la substance contenant
du carbonate de calcium selon la revendication 26 en tant que charge dans le papier.
29. Utilisation selon la revendication 27, dans laquelle la suspension aqueuse de minéral
et/ou charge et/ou pigment riche en solides et/ou la substance contenant du carbonate
de calcium est utilisée comme support pour une impression numérique, une impression
à jet d'encre préférée ou pour une impression flexographique, rotogravure et/ou offset,
de manière préférée entre toutes pour une impression d'encre noire lors d'une impression
à jet d'encre.
30. Formulation de sauce de couchage comprenant la suspension aqueuse de minéral et/ou
charge et/ou pigment riche en solides selon l'une quelconque des revendications 1
à 19 et/ou la substance contenant du carbonate de calcium selon la revendication 26
et un liant naturel et/ou synthétique, le liant se composant de préférence de styrène-butadiène,
styrène-acrylate, acétate de polyvinyle, alcool polyvinylique, amidon ou de mélanges
de ceux-ci, et de manière préférée entre toutes le liant comprend ou se compose d'alcool
polyvinylique.